Catalyst Systems Containing Boron-Bridged Cyclopentadienyl-Fluorenyl Metallocene Compounds With An Alkenyl Substituent

ABSTRACT

Disclosed herein are catalyst compositions containing boron-bridged, cyclopentadienyl-fluorenyl metallocene compounds with an alkenyl substituent. These catalyst compositions can be used for the polymerization of olefins. For example, ethylene copolymers produced using these catalyst compositions can be characterized by a combination of a flat or a conventional comonomer distribution and low levels of long chain branching.

REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Application Ser.No. 61/905,894, filed on Nov. 19, 2013, the disclosure of which isincorporated herein by reference in its entirety.

BACKGROUND OF THE INVENTION

Polyolefins such as high density polyethylene (HDPE) homopolymer andlinear low density polyethylene (LLDPE) copolymer can be produced usingvarious combinations of catalyst systems and polymerization processes.In some end-use applications, it can be beneficial for the polymer tohave a combination of a flat or a conventional comonomer distributionand low levels of long chain branching. Moreover, it can be beneficialfor the catalyst system employed to facilitate good incorporation of acomonomer during polymerization, as well as easy control of themolecular weight distribution with the addition of hydrogen duringpolymerization. Accordingly, it is to these ends that the presentinvention is directed.

SUMMARY OF THE INVENTION

This summary is provided to introduce a selection of concepts in asimplified form that are further described below in the detaileddescription. This summary is not intended to identify required oressential features of the claimed subject matter. Nor is this summaryintended to be used to limit the scope of the claimed subject matter.

The present invention generally relates to new catalyst compositions,methods for preparing the catalyst compositions, methods for using thecatalyst compositions to polymerize olefins, the polymer resins producedusing such catalyst compositions, and articles produced using thesepolymer resins. In particular, the present invention relates toboron-bridged metallocene compounds containing an alkenyl substituent,and to catalyst compositions employing such metallocene compounds.Catalyst compositions of the present invention that contain theseboron-bridged metallocene compounds can be used to produce, for example,ethylene-based homopolymers and copolymers.

In accordance with an aspect of the present invention, disclosed anddescribed herein are boron-bridged metallocene compounds having theformula:

In formula (I), M can be Ti, Zr, or Hf; each X independently can be amonoanionic ligand; Cp^(A) can be a cyclopentadienyl group with analkenyl substituent; Cp^(B) can be a fluorenyl group; and each Rindependently can be H, a C₁ to C₃₆ hydrocarbyl group, or a C₁ to C₃₆hydrocarbylsilyl group.

Catalyst compositions containing the boron-bridged metallocene compoundsof formula (I) also are provided by the present invention. In oneaspect, a catalyst composition is disclosed which comprises aboron-bridged metallocene compound of formula (I) and an activator.Optionally, this catalyst composition can further comprise aco-catalyst, such as an organoaluminum compound. In some aspects, theactivator can comprise an activator-support, while in other aspects, theactivator can comprise an aluminoxane compound, an organoboron ororganoborate compound, an ionizing ionic compound, or combinationsthereof.

The present invention also contemplates and encompasses olefinpolymerization processes. Such processes can comprise contacting acatalyst composition with an olefin monomer and optionally an olefincomonomer in a polymerization reactor system under polymerizationconditions to produce an olefin polymer. Generally, the catalystcomposition employed can comprise any of the boron-bridged metallocenecompounds disclosed herein and any of the activators disclosed herein.Further, organoaluminum compounds or other co-catalysts also can beutilized in the catalyst compositions and/or polymerization processes.

Polymers produced from the polymerization of olefins, resulting inhomopolymers, copolymers, terpolymers, etc., can be used to producevarious articles of manufacture.

Both the foregoing summary and the following detailed descriptionprovide examples and are explanatory only. Accordingly, the foregoingsummary and the following detailed description should not be consideredto be restrictive. Further, features or variations may be provided inaddition to those set forth herein. For example, certain aspects andembodiments may be directed to various feature combinations andsub-combinations described in the detailed description.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 presents a plot of the molecular weight distribution and shortchain branch distribution of the polymer of Example 6.

FIG. 2 presents a plot of the molecular weight distribution and shortchain branch distribution of the polymer of Example 7.

FIG. 3 presents a plot of the molecular weight distribution and shortchain branch distribution of the polymer of Example 8.

FIG. 4 presents a plot of the molecular weight distribution and shortchain branch distribution of the polymer of Example 9.

FIG. 5 presents a plot of the amount of long chain branches (LCB) per1000 total carbon atoms as a function of the molecular weight of thepolymer of Example 10.

FIG. 6 presents a plot of the molecular weight distributions of thepolymers of Examples 11-13, produced with different amounts of hydrogenpresent during polymerization.

DEFINITIONS

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2nd Ed (1997), can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied. To the extent that any definitionor usage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

While compositions and methods are described herein in terms of“comprising” various components or steps, the compositions and methodscan also “consist essentially of” or “consist of” the various componentsor steps, unless stated otherwise. For example, a catalyst compositionconsistent with aspects of the present invention can comprise;alternatively, can consist essentially of; or alternatively, can consistof; (i) a boron-bridged metallocene compound, (ii) an activator, and(iii) optionally, a co-catalyst.

The terms “a,” “an,” “the,” etc., are intended to include pluralalternatives, e.g., at least one, unless otherwise specified. Forinstance, the disclosure of “an activator-support” or “a metallocenecompound” is meant to encompass one, or mixtures or combinations of morethan one, activator-support or metallocene compound, respectively,unless otherwise specified.

Generally, groups of elements are indicated using the numbering schemeindicated in the version of the periodic table of elements published inChemical and Engineering News, 63(5), 27, 1985. In some instances, agroup of elements can be indicated using a common name assigned to thegroup; for example, alkali metals for Group 1 elements, alkaline earthmetals for Group 2 elements, transition metals for Group 3-12 elements,and halogens or halides for Group 17 elements.

For any particular compound disclosed herein, the general structure orname presented is also intended to encompass all structural isomers,conformational isomers, and stereoisomers that can arise from aparticular set of substituents, unless indicated otherwise. Thus, ageneral reference to a compound includes all structural isomers unlessexplicitly indicated otherwise; e.g., a general reference to pentaneincludes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane, while ageneral reference to a butyl group includes an n-butyl group, asec-butyl group, an iso-butyl group, and a tert-butyl group.Additionally, the reference to a general structure or name encompassesall enantiomers, diastereomers, and other optical isomers whether inenantiomeric or racemic forms, as well as mixtures of stereoisomers, asthe context permits or requires. For any particular formula or name thatis presented, any general formula or name presented also encompasses allconformational isomers, regioisomers, and stereoisomers that can arisefrom a particular set of substituents.

The term “substituted” when used to describe a group, for example, whenreferring to a substituted analog of a particular group, is intended todescribe any non-hydrogen moiety that formally replaces a hydrogen inthat group, and is intended to be non-limiting. A group or groups canalso be referred to herein as “unsubstituted” or by equivalent termssuch as “non-substituted,” which refers to the original group in which anon-hydrogen moiety does not replace a hydrogen within that group.Unless otherwise specified, “substituted” is intended to be non-limitingand include inorganic substituents or organic substituents as understoodby one of ordinary skill in the art.

The term “hydrocarbon” whenever used in this specification and claimsrefers to a compound containing only carbon and hydrogen. Otheridentifiers can be utilized to indicate the presence of particulargroups in the hydrocarbon (e.g., halogenated hydrocarbon indicates thepresence of one or more halogen atoms replacing an equivalent number ofhydrogen atoms in the hydrocarbon). The term “hydrocarbyl group” is usedherein in accordance with the definition specified by IUPAC: a univalentgroup formed by removing a hydrogen atom from a hydrocarbon (that is, agroup containing only carbon and hydrogen). Non-limiting examples ofhydrocarbyl groups include alkyl, alkenyl, aryl, and aralkyl groups,amongst other groups.

The term “polymer” is used herein generically to include olefinhomopolymers, copolymers, terpolymers, and so forth. A copolymer isderived from an olefin monomer and one olefin comonomer, while aterpolymer is derived from an olefin monomer and two olefin comonomers.Accordingly, “polymer” encompasses copolymers, terpolymers, etc.,derived from any olefin monomer and comonomer(s) disclosed herein.Similarly, an ethylene polymer would include ethylene homopolymers,ethylene copolymers, ethylene terpolymers, and the like. As an example,an olefin copolymer, such as an ethylene copolymer, can be derived fromethylene and a comonomer, such as 1-butene, 1-hexene, or 1-octene. Ifthe monomer and comonomer were ethylene and 1-hexene, respectively, theresulting polymer can be categorized an as ethylene/1-hexene copolymer.

In like manner, the scope of the term “polymerization” includeshomopolymerization, copolymerization, terpolymerization, etc. Therefore,a copolymerization process can involve contacting one olefin monomer(e.g., ethylene) and one olefin comonomer (e.g., 1-hexene) to produce acopolymer.

The term “co-catalyst” is used generally herein to refer to compoundssuch as aluminoxane compounds, organoboron or organoborate compounds,ionizing ionic compounds, organoaluminum compounds, organozinccompounds, organomagnesium compounds, organolithium compounds, and thelike, that can constitute one component of a catalyst composition, whenused, for example, in addition to an activator-support. The term“co-catalyst” is used regardless of the actual function of the compoundor any chemical mechanism by which the compound may operate.

The terms “chemically-treated solid oxide,” “treated solid oxidecompound,” and the like, are used herein to indicate a solid, inorganicoxide of relatively high porosity, which can exhibit Lewis acidic orBronsted acidic behavior, and which has been treated with anelectron-withdrawing component, typically an anion, and which iscalcined. The electron-withdrawing component is typically anelectron-withdrawing anion source compound. Thus, the chemically-treatedsolid oxide can comprise a calcined contact product of at least onesolid oxide with at least one electron-withdrawing anion sourcecompound. Typically, the chemically-treated solid oxide comprises atleast one acidic solid oxide compound. The “activator-support” of thepresent invention can be a chemically-treated solid oxide. The terms“support” and “activator-support” are not used to imply these componentsare inert, and such components should not be construed as an inertcomponent of the catalyst composition. The term “activator,” as usedherein, refers generally to a substance that is capable of converting ametallocene component into a catalyst that can polymerize olefins, orconverting a contact product of a metallocene component and a componentthat provides an activatable ligand (e.g., an alkyl, a hydride) to themetallocene, when the metallocene compound does not already comprisesuch a ligand, into a catalyst that can polymerize olefins. This term isused regardless of the actual activating mechanism. Illustrativeactivators include activator-supports, aluminoxanes, organoboron ororganoborate compounds, ionizing ionic compounds, and the like.Aluminoxanes, organoboron or organoborate compounds, and ionizing ioniccompounds generally are referred to as activators if used in a catalystcomposition in which an activator-support is not present. If thecatalyst composition contains an activator-support, then thealuminoxane, organoboron or organoborate, and ionizing ionic materialsare typically referred to as co-catalysts.

The term “metallocene” as used herein describes compounds comprising atleast one η³ to η⁵-cycloalkadienyl-type moiety, wherein η³ toη⁵-cycloalkadienyl moieties include cyclopentadienyl ligands, indenylligands, fluorenyl ligands, and the like, including partially saturatedor substituted derivatives or analogs of any of these. Possiblesubstituents on these ligands may include H, therefore this inventioncomprises ligands such as tetrahydroindenyl, tetrahydrofluorenyl,octahydrofluorenyl, partially saturated indenyl, partially saturatedfluorenyl, substituted partially saturated indenyl, substitutedpartially saturated fluorenyl, and the like. In some contexts, themetallocene is referred to simply as the “catalyst,” in much the sameway the term “co-catalyst” is used herein to refer to, for example, anorganoaluminum compound.

The terms “catalyst composition,” “catalyst mixture,” “catalyst system,”and the like, do not depend upon the actual product or compositionresulting from the contact or reaction of the initial components of thedisclosed or claimed catalyst composition/mixture/system, the nature ofthe active catalytic site, or the fate of the co-catalyst, themetallocene compound, or the activator (e.g., activator-support), aftercombining these components. Therefore, the terms “catalyst composition,”“catalyst mixture,” “catalyst system,” and the like, encompass theinitial starting components of the composition, as well as whateverproduct(s) may result from contacting these initial starting components,and this is inclusive of both heterogeneous and homogenous catalystsystems or compositions. The terms “catalyst composition,” “catalystmixture,” “catalyst system,” and the like, can be used interchangeablythroughout this disclosure.

The term “contact product” is used herein to describe compositionswherein the components are contacted together in any order, in anymanner, and for any length of time. For example, the components can becontacted by blending or mixing. Further, contacting of any componentcan occur in the presence or absence of any other component of thecompositions described herein. Combining additional materials orcomponents can be done by any suitable method. Further, the term“contact product” includes mixtures, blends, solutions, slurries,reaction products, and the like, or combinations thereof. Although“contact product” can include reaction products, it is not required forthe respective components to react with one another. Similarly, the term“contacting” is used herein to refer to materials which can be blended,mixed, slurried, dissolved, reacted, treated, or otherwise contacted insome other manner.

Although any methods, devices, and materials similar or equivalent tothose described herein can be used in the practice or testing of theinvention, the typical methods, devices and materials are hereindescribed.

All publications and patents mentioned herein are incorporated herein byreference for the purpose of describing and disclosing, for example, theconstructs and methodologies that are described in the publications,which might be used in connection with the presently describedinvention. The publications discussed throughout the text are providedsolely for their disclosure prior to the filing date of the presentapplication. Nothing herein is to be construed as an admission that theinventors are not entitled to antedate such disclosure by virtue ofprior invention.

Applicants disclose several types of ranges in the present invention.When Applicants disclose or claim a range of any type, Applicants'intent is to disclose or claim individually each possible number thatsuch a range could reasonably encompass, including end points of therange as well as any sub-ranges and combinations of sub-rangesencompassed therein. For example, when the Applicants disclose or claima chemical moiety having a certain number of carbon atoms, Applicants'intent is to disclose or claim individually every possible number thatsuch a range could encompass, consistent with the disclosure herein. Forexample, the disclosure that a moiety is a C₁ to C₁₈ hydrocarbyl group,or in alternative language, a hydrocarbyl group having from 1 to 18carbon atoms, as used herein, refers to a moiety that can have 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms, aswell as any range between these two numbers (for example, a C₁ to C₈hydrocarbyl group), and also including any combination of ranges betweenthese two numbers (for example, a C₂ to C₄ and a C₁₂ to C₁₆ hydrocarbylgroup).

Similarly, another representative example follows for the polydispersityindex, Mw/Mn, of an olefin polymer produced in an aspect of thisinvention. By a disclosure that the ratio of Mw/Mn can be in a rangefrom about 2 to about 12, Applicants intend to recite that the Mw/Mn canbe any ratio in the range and, for example, can be equal to about 2,about 3, about 4, about 5, about 6, about 7, about 8, about 9, about 10,about 11, or about 12. Additionally, the Mw/Mn can be within any rangefrom about 2 to about 12 (for example, from about 2 to about 5), andthis also includes any combination of ranges between about 2 and about12 (for example, the Mw/Mn can be in a range from about 2 to about 4, orfrom about 6 to about 10). Likewise, all other ranges disclosed hereinshould be interpreted in a manner similar to these two examples.

Applicants reserve the right to proviso out or exclude any individualmembers of any such group, including any sub-ranges or combinations ofsub-ranges within the group, that can be claimed according to a range orin any similar manner, if for any reason Applicants choose to claim lessthan the full measure of the disclosure, for example, to account for areference that Applicants may be unaware of at the time of the filing ofthe application. Further, Applicants reserve the right to proviso out orexclude any individual substituents, analogs, compounds, ligands,structures, or groups thereof, or any members of a claimed group, if forany reason Applicants choose to claim less than the full measure of thedisclosure, for example, to account for a reference that Applicants maybe unaware of at the time of the filing of the application.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed generally to new catalystcompositions, methods for preparing the catalyst compositions, methodsfor using the catalyst compositions to polymerize olefins, the polymerresins produced using such catalyst compositions, and articles producedusing these polymer resins. In particular, the present invention relatesto boron-bridged metallocene complexes containing an alkenylsubstituent, to catalyst compositions employing these boron-bridgedmetallocene complexes, to polymerization processes utilizing suchcatalyst compositions, and to the resulting olefin polymers producedfrom the polymerization processes.

Boron-Bridged Metallocenes

The present invention discloses novel boron-bridged metallocenecomplexes or compounds containing an alkenyl substituent, and methods ofmaking these complexes or compounds. In an aspect of this invention, theboron-bridged metallocene compound can have the formula:

Within formula (I), M, Cp^(A), Cp^(B), each X, and each R areindependent elements of the metallocene compound. Accordingly, themetallocene compound having formula (I) may be described using anycombination of M, Cp^(A), Cp^(B), X, and R disclosed herein.

Unless otherwise specified, formula (I) above, any other structuralformulas disclosed herein, and any metallocene complex, compound, orspecies disclosed herein are not designed to show stereochemistry orisomeric positioning of the different moieties (e.g., these formulas arenot intended to display cis or trans isomers, or R or Sdiastereoisomers), although such compounds are contemplated andencompassed by these formulas and/or structures.

In accordance with aspects of this invention, the metal in formula (I),M, can be Ti, Zr, or Hf. In one aspect, for instance, M can be Zr or Hf,while in another aspect, M can be Ti; alternatively, M can be Zr; oralternatively, M can be Hf.

Each X in formula (I) independently can be a monoanionic ligand. In someaspects, suitable monoanionic ligands can include, but are not limitedto, H (hydride), BH₄, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁ toC₃₆ hydrocarboxy group, a C₁ to C₃₆ hydrocarbylaminyl group, a C₁ to C₃₆hydrocarbylsilyl group, a C₁ to C₃₆ hydrocarbylaminylsilyl group, —OBR¹₂, or —OSO₂R¹, wherein R¹ is a C₁ to C₃₆ hydrocarbyl group. It iscontemplated that each X can be either the same or a differentmonoanionic ligand.

In one aspect, each X independently can be H, BH₄, a halide (e.g., F,Cl, Br, etc.), a C₁ to C₁₈ hydrocarbyl group, a C₁ to C₁₈ hydrocarboxygroup, a C₁ to C₁₈ hydrocarbylaminyl group, a C₁ to C₁₈ hydrocarbylsilylgroup, or a C₁ to C₁₈ hydrocarbylaminylsilyl group. Alternatively, eachX independently can be H, BH₄, a halide, OBR¹ ₂, or OSO₂R¹, wherein R¹is a C₁ to C₁₈ hydrocarbyl group. In another aspect, each Xindependently can be H, BH₄, a halide, a C₁ to C₁₂ hydrocarbyl group, aC₁ to C₁₂ hydrocarboxy group, a C₁ to C₁₂ hydrocarbylaminyl group, a C₁to C₁₂ hydrocarbylsilyl group, a C₁ to C₁₂ hydrocarbylaminylsilyl group,OBR¹ ₂, or OSO₂R¹, wherein R¹ is a C₁ to C₁₂ hydrocarbyl group. Inanother aspect, each X independently can be H, BH₄, a halide, a C₁ toC₁₀ hydrocarbyl group, a C₁ to C₁₀ hydrocarboxy group, a C₁ to C₁₀hydrocarbylaminyl group, a C₁ to C₁₀ hydrocarbylsilyl group, a C₁ to C₁₀hydrocarbylaminylsilyl group, OBR¹ ₂, or OSO₂R¹, wherein R¹ is a C₁ toC₁₀ hydrocarbyl group. In yet another aspect, each X independently canbe H, BH₄, a halide, a C₁ to C₈ hydrocarbyl group, a C₁ to C₈hydrocarboxy group, a C₁ to C₈ hydrocarbylaminyl group, a C₁ to C₈hydrocarbylsilyl group, a C₁ to C₈ hydrocarbylaminylsilyl group, OBR¹ ₂,or OSO₂R¹, wherein R¹ is a C₁ to C₈ hydrocarbyl group. In still anotheraspect, each X independently can be a halide or a C₁ to C₁₈ hydrocarbylgroup. For example, both X's can be Cl.

The hydrocarbyl group which can be an X (one or both) in formula (I) canbe a C₁ to C₃₆ hydrocarbyl group, including, but not limited to, a C₁ toC₃₆ alkyl group, a C₂ to C₃₆ alkenyl group, a C₄ to C₃₆ cycloalkylgroup, a C₆ to C₃₆ aryl group, or a C₇ to C₃₆ aralkyl group. Forinstance, each X independently can be a C₁ to C₁₈ alkyl group, a C₂ toC18 alkenyl group, a C₄ to C₁₈ cycloalkyl group, a C₆ to C₁₈ aryl group,or a C₇ to C₁₈ aralkyl group; alternatively, each X independently can bea C₁ to C₁₂ alkyl group, a C₂ to C₁₂ alkenyl group, a C₄ to C₁₂cycloalkyl group, a C₆ to C₁₂ aryl group, or a C₇ to C₁₂ aralkyl group;alternatively, each X independently can be a C₁ to C₁₀ alkyl group, a C₂to C₁₀ alkenyl group, a C₄ to C₁₀ cycloalkyl group, a C₆ to C₁₀ arylgroup, or a C₇ to C₁₀ aralkyl group; or alternatively, each Xindependently can be a C₁ to C₅ alkyl group, a C₂ to C₅ alkenyl group, aC₅ to C₈ cycloalkyl group, a C₆ to C₈ aryl group, or a C₇ to C₈ aralkylgroup.

Accordingly, in some aspects, the alkyl group which can be an X informula (I) can be a methyl group, an ethyl group, a propyl group, abutyl group, a pentyl group, a hexyl group, a heptyl group, an octylgroup, a nonyl group, a decyl group, a undecyl group, a dodecyl group, atridecyl group, a tetradecyl group, a pentadecyl group, a hexadecylgroup, a heptadecyl group, or an octadecyl group; or alternatively, amethyl group, an ethyl group, a propyl group, a butyl group, a pentylgroup, a hexyl group, a heptyl group, an octyl group, a nonyl group, ora decyl group. In some aspects, the alkyl group which can be an X informula (I) can be a methyl group, an ethyl group, a n-propyl group, aniso-propyl group, a n-butyl group, an iso-butyl group, a sec-butylgroup, a tert-butyl group, a n-pentyl group, an iso-pentyl group, asec-pentyl group, or a neopentyl group; alternatively, a methyl group,an ethyl group, an iso-propyl group, a tert-butyl group, or a neopentylgroup; alternatively, a methyl group; alternatively, an ethyl group;alternatively, a n-propyl group; alternatively, an iso-propyl group;alternatively, a tert-butyl group; or alternatively, a neopentyl group.

Suitable alkenyl groups which can be an X in formula (I) can include,but are not limited to, an ethenyl group, a propenyl group, a butenylgroup, a pentenyl group, a hexenyl group, a heptenyl group, an octenylgroup, a nonenyl group, a decenyl group, a undecenyl group, a dodecenylgroup, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, ahexadecenyl group, a heptadecenyl group, or an octadecenyl group. Suchalkenyl groups can be linear or branched, and the double bond can belocated anywhere in the chain. In one aspect, each X in formula (I)independently can be an ethenyl group, a propenyl group, a butenylgroup, a pentenyl group, a hexenyl group, a heptenyl group, an octenylgroup, a nonenyl group, or a decenyl group, while in another aspect,each X in formula (I) independently can be an ethenyl group, a propenylgroup, a butenyl group, a pentenyl group, or a hexenyl group. Forexample, an X can be an ethenyl group; alternatively, a propenyl group;alternatively, a butenyl group; alternatively, a pentenyl group; oralternatively, a hexenyl group. In yet another aspect, an X can be aterminal alkenyl group, such as a C₃ to C₁₈ terminal alkenyl group, a C₃to C₁₂ terminal alkenyl group, or a C₃ to C₈ terminal alkenyl group.Illustrative terminal alkenyl groups can include, but are not limitedto, a prop-2-en-1-yl group, a bute-3-en-1-yl group, a pent-4-en-1-ylgroup, a hex-5-en-1-yl group, a hept-6-en-1-yl group, an octe-7-en-1-ylgroup, a non-8-en-1-yl group, a dece-9-en-1-yl group, and so forth.

Each X in formula (I) independently can be a cycloalkyl group,including, but not limited to, a cyclobutyl group, a substitutedcyclobutyl group, a cyclopentyl group, a substituted cyclopentyl group,a cyclohexyl group, a substituted cyclohexyl group, a cycloheptyl group,a substituted cycloheptyl group, a cyclooctyl group, or a substitutedcyclooctyl group. For example, an X in formula (I) can be a cyclopentylgroup, a substituted cyclopentyl group, a cyclohexyl group, or asubstituted cyclohexyl group. Moreover, each X in formula (I)independently can be a cyclobutyl group or a substituted cyclobutylgroup; alternatively, a cyclopentyl group or a substituted cyclopentylgroup; alternatively, a cyclohexyl group or a substituted cyclohexylgroup; alternatively, a cycloheptyl group or a substituted cycloheptylgroup; alternatively, a cyclooctyl group or a substituted cyclooctylgroup; alternatively, a cyclopentyl group; alternatively, a substitutedcyclopentyl group; alternatively, a cyclohexyl group; or alternatively,a substituted cyclohexyl group. Substituents which can be utilized forthe substituted cycloalkyl group are independently disclosed herein andcan be utilized without limitation to further describe the substitutedcycloalkyl group which can be an X in formula (I).

In some aspects, the aryl group which can be an X in formula (I) can bea phenyl group, a substituted phenyl group, a naphthyl group, or asubstituted naphthyl group. In an aspect, the aryl group can be a phenylgroup or a substituted phenyl group; alternatively, a naphthyl group ora substituted naphthyl group; alternatively, a phenyl group or anaphthyl group; alternatively, a substituted phenyl group or asubstituted naphthyl group; alternatively, a phenyl group; oralternatively, a naphthyl group. Substituents which can be utilized forthe substituted phenyl groups or substituted naphthyl groups areindependently disclosed herein and can be utilized without limitation tofurther describe the substituted phenyl groups or substituted naphthylgroups which can be an X in formula (I).

In an aspect, the substituted phenyl group which can be an X in formula(I) can be a 2-substituted phenyl group, a 3-substituted phenyl group, a4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, a 3,5-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group. In other aspects, the substitutedphenyl group can be a 2-substituted phenyl group, a 4-substituted phenylgroup, a 2,4-disubstituted phenyl group, or a 2,6-disubstituted phenylgroup; alternatively, a 3-substituted phenyl group or a3,5-disubstituted phenyl group; alternatively, a 2-substituted phenylgroup or a 4-substituted phenyl group; alternatively, a2,4-disubstituted phenyl group or a 2,6-disubstituted phenyl group;alternatively, a 2-substituted phenyl group; alternatively, a3-substituted phenyl group; alternatively, a 4-substituted phenyl group;alternatively, a 2,4-disubstituted phenyl group; alternatively, a2,6-disubstituted phenyl group; alternatively, a 3,5-disubstitutedphenyl group; or alternatively, a 2,4,6-trisubstituted phenyl group.Substituents which can be utilized for these specific substituted phenylgroups are independently disclosed herein and can be utilized withoutlimitation to further describe these substituted phenyl groups which canbe an X in formula (I).

In some aspects, the aralkyl group which can be an X in formula (I) canbe a benzyl group or a substituted benzyl group. In an aspect, thearalkyl group can be a benzyl group or, alternatively, a substitutedbenzyl group. Substituents which can be utilized for the substitutedaralkyl group are independently disclosed herein and can be utilizedwithout limitation to further describe the substituted aralkyl groupwhich can be an X in formula (I).

In an aspect, each non-hydrogen substituent(s) for the substitutedcycloalkyl group, substituted aryl group, or substituted aralkyl groupwhich can be an X in formula (I) independently can be a C₁ to C₁₈hydrocarbyl group; alternatively, a C₁ to C₈ hydrocarbyl group; oralternatively, a C₁ to C₅ hydrocarbyl group. Specific hydrocarbyl groupsare independently disclosed herein and can be utilized withoutlimitation to further describe the substituents of the substitutedcycloalkyl groups, substituted aryl groups, or substituted aralkylgroups which can be an X in formula (I). For instance, the hydrocarbylsubstituent can be an alkyl group, such as a methyl group, an ethylgroup, a n-propyl group, an isopropyl group, a n-butyl group, asec-butyl group, an isobutyl group, a tert-butyl group, a n-pentylgroup, a 2-pentyl group, a 3-pentyl group, a 2-methyl-1-butyl group, atert-pentyl group, a 3-methyl-1-butyl group, a 3-methyl-2-butyl group,or a neo-pentyl group, and the like. Furthermore, the hydrocarbylsubstituent can be a benzyl group, a phenyl group, a tolyl group, or axylyl group, and the like.

A hydrocarboxy group is used generically herein to include, forinstance, alkoxy, aryloxy, aralkoxy, -(alkyl, aryl, oraralkyl)-O-(alkyl, aryl, or aralkyl) groups, and —O(CO)-(hydrogen orhydrocarbyl) groups, and these groups can comprise up to about 36 carbonatoms (e.g., C₁ to C₃₆, C₁ to C₁₈, C₁ to C₁₀, or C₁ to C₈ hydrocarboxygroups). Illustrative and non-limiting examples of hydrocarboxy groupswhich can be an X in formula (I) can include, but are not limited to, amethoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group,an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxygroup, an n-pentoxy group, a 2-pentoxy group, a 3-pentoxy group, a2-methyl-l-butoxy group, a tert-pentoxy group, a 3-methyl-1-butoxygroup, a 3-methyl-2-butoxy group, a neo-pentoxy group, a phenoxy group,a toloxy group, a xyloxy group, a 2,4,6-trimethylphenoxy group, abenzoxy group, an acetylacetonate group (acac), a formate group, anacetate group, a stearate group, an oleate group, a benzoate group, andthe like. In an aspect, the hydrocarboxy group which can be an X informula (I) can be a methoxy group; alternatively, an ethoxy group;alternatively, an n-propoxy group; alternatively, an isopropoxy group;alternatively, an n-butoxy group; alternatively, a sec-butoxy group;alternatively, an isobutoxy group; alternatively, a tert-butoxy group;alternatively, an n-pentoxy group; alternatively, a 2-pentoxy group;alternatively, a 3-pentoxy group; alternatively, a 2-methyl-1-butoxygroup; alternatively, a tert-pentoxy group; alternatively, a3-methyl-1-butoxy group, alternatively, a 3-methyl-2-butoxy group;alternatively, a neo-pentoxy group; alternatively, a phenoxy group;alternatively, a toloxy group; alternatively, a xyloxy group;alternatively, a 2,4,6-trimethylphenoxy group; alternatively, a benzoxygroup; alternatively, an acetylacetonate group; alternatively, a formategroup; alternatively, an acetate group; alternatively, a stearate group;alternatively, an oleate group; or alternatively, a benzoate group.

The term hydrocarbylaminyl group is used generically herein to refercollectively to, for instance, alkylaminyl, arylaminyl, aralkylaminyl,dialkylaminyl, diarylaminyl, diaralkylaminyl, and -(alkyl, aryl, oraralkyl)-N-(alkyl, aryl, or aralkyl) groups, and unless otherwisespecified, the hydrocarbylaminyl groups which can be an X in formula (I)can comprise up to about 36 carbon atoms (e.g., C₁ to C₃₆, C₁ to C₁₈, C₁to C₁₀, or C₁ to C₈ hydrocarbylaminyl groups). Accordingly,hydrocarbylaminyl is intended to cover both (mono)hydrocarbylaminyl anddihydrocarbylaminyl groups. In some aspects, the hydrocarbylaminyl groupwhich can be an X in formula (I) can be, for instance, a methylaminylgroup (—NHCH₃), an ethylaminyl group (—NHCH₂CH₃), an n-propylaminylgroup (—NHCH₂CH₂CH₃), an iso-propylaminyl group (—NHCH(CH₃)₂), ann-butylaminyl group (—NHCH₂CH₂CH₂CH₃), a t-butylaminyl group(—NHC(CH₃)₃), an n-pentylaminyl group (—NHCH₂CH₂CH₂CH₂CH₃), aneo-pentylaminyl group (—NHCH₂C(CH₃)₃), a phenylaminyl group (—NHC₆H₅),a tolylaminyl group (—NHC₆H₄CH₃), or a xylylaminyl group(—NHC₆H₃(CH₃)₂); alternatively, a methylaminyl group; alternatively, anethylaminyl group; alternatively, a propylaminyl group; oralternatively, a phenylaminyl group. In other aspects, thehydrocarbylaminyl group which can be an X in formula (I) can be, forinstance, a dimethylaminyl group (—N(CH₃)₂), a diethylaminyl group(—N(CH₂CH₃)₂), a di-n-propylaminyl group (—N(CH₂CH₂CH₃)₂), adi-iso-propylaminyl group (—N(CH(CH₃)₂)₂), a di-n-butylaminyl group(—N(CH₂CH₂CH₂CH₃)₂), a di-t-butylaminyl group (—N(C(CH₃)₃)₂), adi-n-pentylaminyl group (—N(CH₂CH₂CH₂CH₂CH₃)₂), a di-neo-pentylaminylgroup (—N(CH₂C(CH₃)₃)₂), a di-phenylaminyl group (—N(C₆H₅)₂), adi-tolylaminyl group (—N(C₆H₄CH₃)₂), or a di-xylylaminyl group(—N(C₆H₃(CH₃)₂)₂); alternatively, a dimethylaminyl group; alternatively,a di-ethylaminyl group; alternatively, a di-n-propylaminyl group; oralternatively, a di-phenylaminyl group.

In accordance with some aspects disclosed herein, each X independentlycan be a C₁ to C₃₆ hydrocarbylsilyl group; alternatively, a C₁ to C₂₄hydrocarbylsilyl group; alternatively, a C₁ to C₁₈ hydrocarbylsilylgroup; or alternatively, a C₁ to C₈ hydrocarbylsilyl group. In anaspect, each hydrocarbyl (one or more) of the hydrocarbylsilyl group canbe any hydrocarbyl group disclosed herein (e.g., a C₁ to C₅ alkyl group,a C₂ to C₅ alkenyl group, a C₅ to C₈ cycloalkyl group, a C₆ to C₈ arylgroup, a C₇ to C₈ aralkyl group, etc.). As used herein, hydrocarbylsilylis intended to cover (mono)hydrocarbylsilyl (—SiH₂R), dihydrocarbylsilyl(—SiHR₂), and trihydrocarbylsilyl (—SiR₃) groups, with R being ahydrocarbyl group. In one aspect, the hydrocarbylsilyl group can be a C₃to C₃₆ or a C₃ to C₁₈ trihydrocarbylsilyl group, such as, for example, atrialkylsilyl group or a triphenylsilyl group. Illustrative andnon-limiting examples of hydrocarbylsilyl groups which can be an X informula (I) can include, but are not limited to, trimethylsilyl,triethylsilyl, tripropylsilyl (e.g., triisopropylsilyl), tributylsilyl,tripentylsilyl, triphenylsilyl, allyldimethylsilyl, and the like.

A hydrocarbylaminylsilyl group is used herein to refer to groupscontaining at least one hydrocarbon moiety, at least one N atom, and atleast one Si atom. Illustrative and non-limiting examples ofhydrocarbylaminylsilyl groups which can be an X include, but are notlimited to, —N(SiMe₃)₂, —N(SiEt₃)₂, and the like. Unless otherwisespecified, the hydrocarbylaminylsilyl groups which can be an X cancomprise up to about 36 carbon atoms (e.g., C₁ to C₃₆, C₁ to C₁₈, C₁ toC₁₂, or C₁ to C₈ hydrocarbylaminylsilyl groups). In an aspect, eachhydrocarbyl (one or more) of the hydrocarbylaminylsilyl group can be anyhydrocarbyl group disclosed herein (e.g., a C₁ to C₅ alkyl group, a C₂to C₅ alkenyl group, a C₅ to C₈ cycloalkyl group, a C₆ to C₈ aryl group,a C₇ to C₈ aralkyl group, etc.). Moreover, hydrocarbylaminylsilyl isintended to cover —NH(SiH₂R), —NH(SiHR₂), —NH(SiR₃), —N(SiH₂R)₂,—N(SiHR₂)₂, and —N(SiR₃)₂ groups, among others, with R being ahydrocarbyl group.

In an aspect, each X independently can be —OBR¹ ₂ or —OSO₂R¹, wherein R¹is a C₁ to C₃₆ hydrocarbyl group, or alternatively, a C₁ to C₁₈hydrocarbyl group. The hydrocarbyl group in OBR¹ ₂ and/or OSO₂R¹independently can be any hydrocarbyl group disclosed herein, such as,for instance, a C₁ to C₁₈ alkyl group, a C₂ to C₁₈ alkenyl group, a C₄to C₁₈ cycloalkyl group, a C₆ to C₁₈ aryl group, or a C₇ to C₁₈ aralkylgroup; alternatively, a C₁ to C₁₂ alkyl group, a C₂ to C₁₂ alkenylgroup, a C₄ to C₁₂ cycloalkyl group, a C₆ to C₁₂ aryl group, or a C₇ toC₁₂ aralkyl group; or alternatively, a C₁ to C₈ alkyl group, a C₂ to C₈alkenyl group, a C₅ to C₈ cycloalkyl group, a C₆ to C₈ aryl group, or aC₇ to C₈ aralkyl group.

In one aspect, each X independently can be H, BH₄, a halide, or a C₁ toC₃₆ hydrocarbyl group, hydrocarboxy group, hydrocarbylaminyl group,hydrocarbylsilyl group, or hydrocarbylaminylsilyl group, while inanother aspect, each X independently can be H, BH₄, or a C₁ to C₁₈hydrocarboxy group, hydrocarbylaminyl group, hydrocarbylsilyl group, orhydrocarbylaminylsilyl group. In yet another aspect, each Xindependently can be a halide; alternatively, a C₁ to C₁₈ hydrocarbylgroup; alternatively, a C₁ to C₁₈ hydrocarboxy group; alternatively, aC₁ to C₁₈ hydrocarbylaminyl group; alternatively, a C₁ to C₁₈hydrocarbylsilyl group; or alternatively, a C₁ to C₁₈hydrocarbylaminylsilyl group. In still another aspect, both X's can beH; alternatively, F; alternatively, Cl; alternatively, Br;alternatively, I; alternatively, BH₄; alternatively, a C₁ to C₁₈hydrocarbyl group; alternatively, a C₁ to C₁₈ hydrocarboxy group;alternatively, a C₁ to C₁₈ hydrocarbylaminyl group; alternatively, a C₁to C₁₈ hydrocarbylsilyl group; or alternatively, a C₁ to C₁₈hydrocarbylaminylsilyl group.

Each X independently can be, in some aspects, H, a halide, methyl,phenyl, benzyl, an alkoxy, an aryloxy, acetylacetonate, formate,acetate, stearate, oleate, benzoate, an alkylaminyl, a dialkylaminyl, atrihydrocarbylsilyl, or a hydrocarbylaminylsilyl; alternatively, H, ahalide, methyl, phenyl, or benzyl; alternatively, an alkoxy, an aryloxy,or acetylacetonate; alternatively, an alkylaminyl or a dialkylaminyl;alternatively, a trihydrocarbylsilyl or hydrocarbylaminylsilyl;alternatively, H or a halide; alternatively, methyl, phenyl, benzyl, analkoxy, an aryloxy, acetylacetonate, an alkylaminyl, or a dialkylaminyl;alternatively, H; alternatively, a halide; alternatively, methyl;alternatively, phenyl; alternatively, benzyl; alternatively, an alkoxy;alternatively, an aryloxy; alternatively, acetylacetonate;alternatively, an alkylaminyl; alternatively, a dialkylaminyl;alternatively, a trihydrocarbylsilyl; or alternatively, ahydrocarbylaminylsilyl. In these and other aspects, the alkoxy, aryloxy,alkylaminyl, dialkylaminyl, trihydrocarbylsilyl, andhydrocarbylaminylsilyl can be a C₁ to C₃₆, a C₁ to C₁₈, a C₁ to C₁₂, ora C₁ to C₈ alkoxy, aryloxy, alkylaminyl, dialkylaminyl,trihydrocarbylsilyl, and hydrocarbylaminylsilyl.

Moreover, each X independently can be, in certain aspects, a halide or aC₁ to C₁₈ hydrocarbyl group; alternatively, a halide or a C₁ to C₈hydrocarbyl group; alternatively, F, Cl, Br, I, methyl, benzyl, orphenyl; alternatively, Cl, methyl, benzyl, or phenyl; alternatively, aC₁ to C₁₈ alkoxy, aryloxy, alkylaminyl, dialkylaminyl,trihydrocarbylsilyl, or hydrocarbylaminylsilyl group; alternatively, aC₁ to C₈ alkoxy, aryloxy, alkylaminyl, dialkylaminyl,trihydrocarbylsilyl, or hydrocarbylaminylsilyl group; or alternatively,methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl,nonenyl, decenyl, phenyl, tolyl, benzyl, naphthyl, trimethylsilyl,triisopropylsilyl, triphenylsilyl, or allyldimethylsilyl.

In formula (I), Cp^(A) can be a cyclopentadienyl group with an alkenylsubstituent, and Cp^(B) can be a fluorenyl group. The alkenylsubstituent can be at any suitable position(s) on Cp^(A) that conformsto the rules of chemical valence. In some aspects, Cp^(A) has only onesubstituent, and that one substituent is the alkenyl substituent.

In one aspect, the alkenyl substituent can be a C₂ to C₁₈ alkenyl group,i.e., any C₂ to C₁₈ alkenyl group disclosed herein. In another aspect,the alkenyl substituent can be an ethenyl group, a propenyl group, abutenyl group, a pentenyl group, a hexenyl group, a heptenyl group, anoctenyl group, a nonenyl group, or a decenyl group. In yet anotheraspect, the alkenyl substituent can be a C₂ to C₁₂ linear or branchedalkenyl group; alternatively, a C₂ to C₈ linear or branched alkenylgroup; alternatively, a C₃ to C₁₂ linear alkenyl group; alternatively, aC₂ to C₈ linear alkenyl group; alternatively, a C2 to C8 terminalalkenyl group; or alternatively, a C₃ to C₆ terminal alkenyl group.

In accordance with non-limiting aspects of this invention, Cp^(A) can bea cyclopentadienyl group with only an alkenyl substituent, and Cp^(B)can be a fluorenyl group that does not contain any substituents; orCp^(A) can be a cyclopentadienyl group with an alkenyl substituent andone or more other substituents, and Cp^(B) can be a fluorenyl group thatdoes not contain an alkenyl substituent, but contains one or more othersubstituents; or Cp^(A) can be a cyclopentadienyl group with an alkenylsubstituent and one or more other substituents, and Cp^(B) can be afluorenyl group that does not contain any substituents; or Cp^(A) can bea cyclopentadienyl group with only an alkenyl substituent, and Cp^(B)can be a fluorenyl group that contains one or more substituents.

In some aspects, Cp^(A) can contain a substituent (one or more) inaddition to the alkenyl substituent, e.g., H, a halide, a C₁ to C₃₆hydrocarbyl group, a C₁ to C₃₆ halogenated hydrocarbyl group, a C₁ toC₃₆ hydrocarboxy group, or a C₁ to C₃₆ hydrocarbylsilyl group.Similarly, Cp^(B) can contain a substituent (one or more), e.g., H, ahalide, a C₁ to C₃₆ hydrocarbyl group, a C₁ to C₃₆ halogenatedhydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, or a C₁ to C₃₆hydrocarbylsilyl group. Hence, each substituent independently can be H;alternatively, a halide; alternatively, a C₁ to C₁₈ hydrocarbyl group;alternatively, a C₁ to C₁₈ halogenated hydrocarbyl group; alternatively,a C₁ to C₁₈ hydrocarboxy group; alternatively, a C₁ to C₁₈hydrocarbylsilyl group; alternatively, a C₁ to C₁₂ hydrocarbyl group ora C₁ to C₁₂ hydrocarbylsilyl group; or alternatively, a C₁ to C₈ alkylgroup or a C₃ to C₈ alkenyl group. The halide, C₁ to C₃₆ hydrocarbylgroup, C₁ to C₃₆ hydrocarboxy group, and C₁ to C₃₆ hydrocarbylsilylgroup which can be a substituent on Cp^(A) and/or Cp^(B) in formula (I)can be any halide, C₁ to C₃₆ hydrocarbyl group, C₁ to C₃₆ hydrocarboxygroup, and C₁ to C₃₆ hydrocarbylsilyl group described herein (e.g., aspertaining to X in formula (I)). A substituent on Cp^(A) and/or Cp^(B)independently can be, in certain aspects, a C₁ to C₃₆ halogenatedhydrocarbyl group, where the halogenated hydrocarbyl group indicates thepresence of one or more halogen atoms replacing an equivalent number ofhydrogen atoms in the hydrocarbyl group. The halogenated hydrocarbylgroup often can be a halogenated alkyl group, a halogenated alkenylgroup, a halogenated cycloalkyl group, a halogenated aryl group, or ahalogenated aralkyl group. Representative and non-limiting halogenatedhydrocarbyl groups include pentafluorophenyl, trifluoromethyl (CF₃), andthe like.

As a non-limiting example, each substituent on Cp^(A) and/or Cp^(B)independently can be H, Cl, CF₃, a methyl group, an ethyl group, apropyl group, a butyl group (e.g., t-Bu), a pentyl group, a hexyl group,a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenylgroup, a propenyl group, a butenyl group, a pentenyl group, a hexenylgroup, a heptenyl group, an octenyl group, a nonenyl group, a decenylgroup, a phenyl group, a tolyl group (or other substituted aryl group),a benzyl group, a naphthyl group, a trimethylsilyl group, atriisopropylsilyl group, a triphenylsilyl group, an allyldimethylsilylgroup, or a 1-methylcyclohexyl group; alternatively, H; alternatively,Cl; alternatively, CF₃; alternatively, a methyl group; alternatively, anethyl group; alternatively, a propyl group; alternatively, a butylgroup; alternatively, a pentyl group; alternatively, a hexyl group;alternatively, a heptyl group; alternatively, an octyl group, a nonylgroup; alternatively, a decyl group; alternatively, an ethenyl group;alternatively, a propenyl group; alternatively, a butenyl group;alternatively, a pentenyl group; alternatively, a hexenyl group;alternatively, a heptenyl group; alternatively, an octenyl group;alternatively, a nonenyl group; alternatively, a decenyl group;alternatively, a phenyl group; alternatively, a tolyl group;alternatively, a benzyl group; alternatively, a naphthyl group;alternatively, a trimethylsilyl group; alternatively, atriisopropylsilyl group; alternatively, a triphenylsilyl group;alternatively, an allyldimethylsilyl group; or alternatively, a1-methylcyclohexyl group.

In one aspect, for example, each substituent on Cp^(A) and/or Cp^(B)independently can be H or a C₁ to C₁₈ hydrocarbyl group; alternatively,a C₁ to C₁₀ hydrocarbyl group; alternatively, a C₁ to C₆ linear orbranched alkyl group (e.g., a tert-butyl group); alternatively, H, Cl,CF₃, a methyl group, an ethyl group, a propyl group, a butyl group(e.g., t-Bu), a pentyl group, a hexyl group, a heptyl group, an octylgroup, a nonyl group, a decyl group, an ethenyl group, a propenyl group,a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, anoctenyl group, a nonenyl group, a decenyl group, a phenyl group, a tolylgroup, a benzyl group, a naphthyl group, a trimethylsilyl group, atriisopropylsilyl group, a triphenylsilyl group, an allyldimethylsilylgroup, or a 1-methylcyclohexyl group, and the like; alternatively, amethyl group, an ethyl group, a propyl group, a butyl group, a pentylgroup, a hexyl group, a heptyl group, an octyl group, a nonyl group, adecyl group, an ethenyl group, a propenyl group, a butenyl group, apentenyl group, a hexenyl group, a heptenyl group, an octenyl group, anonenyl group, a decenyl group, a phenyl group, a tolyl group, or abenzyl group; alternatively, a methyl group, an ethyl group, a propylgroup, a butyl group, a pentyl group, or a hexyl group; alternatively, amethyl group; alternatively, an ethyl group; alternatively, a propylgroup; alternatively, a butyl group; or alternatively, a tert-butylgroup.

In formula (I), each R independently can be H, a C₁ to C₃₆ hydrocarbylgroup, or a C₁ to C₃₆ hydrocarbylsilyl group. The C₁ to C₃₆ hydrocarbylgroup and C₁ to C₃₆ hydrocarbylsilyl group which can be a R in formula(I) can be any C₁ to C₃₆ hydrocarbyl group or C₁ to C₃₆ hydrocarbylsilylgroup described herein (e.g., as pertaining to X in formula (I)). It iscontemplated that each R can be either the same or a differentsubstituent group. For example, each R independently can be H, a C₁ toC₁₈ hydrocarbyl group, or a C₁ to C₁₈ hydrocarbylsilyl group. In someaspects, each R independently can be a C₁ to C₆ linear or branched alkylgroup (e.g., an isopropyl group). In other aspects, each R independentlycan be a methyl group, an ethyl group, a propyl group, a butyl group, apentyl group, a hexyl group, a heptyl group, an octyl group, a nonylgroup, a decyl group, a phenyl group, a tolyl group, a benzyl group, anaphthyl group, a trimethylsilyl group, a triisopropylsilyl group, atriphenylsilyl group, an allyldimethylsilyl group, or a1-methylcyclohexyl group, and the like.

Illustrative and non-limiting examples of boron-bridged metallocenecompounds with an alkenyl substituent can include the followingcompounds:

and the like.

Methods of making boron-bridged metallocene complexes of the presentinvention also are encompassed herein. These metallocene complexes canbe synthesized by various suitable procedures, such as those describedin WO 00/20462, the disclosure of which is incorporated herein byreference in its entirety, and the procedures provided herein. Arepresentative synthesis scheme is provided below, wherein theboron-bridged metallocene compound is synthesized in a multistep processfrom dichloro(diisopropylamino)borane.

Also encompassed herein are ligand compounds which can be used to formmetallocene compounds having formula (I). Such ligand compounds can havethe formula:

The selections for Cp^(A), Cp^(B), and each R in formula (A) are thesame as those described herein above for formula (I). Hence, in formula(A), Cp^(A) can be a cyclopentadienyl group with an alkenyl substituent,Cp^(B) can be a fluorenyl group, and each R independently can be H, orany C₁ to C₃₆ hydrocarbyl group or C₁ to C₃₆ hydrocarbylsilyl groupdisclosed herein.

Illustrative and non-limiting examples of cyclopentadienyl-indenylboron-bridged ligand compounds (with the alkenyl substituent on thecyclopentadienyl group) can include the following compounds:

and the like.

Illustrative and non-limiting examples of cyclopentadienyl-fluorenylboron-bridged ligand compounds (with the alkenyl substituent on thecyclopentadienyl group) can include the following compounds:

and the like.

Illustrative and non-limiting examples of indenyl-indenyl boron-bridgedligand compounds (with the alkenyl substituent on an indenyl group) caninclude the following compounds:

and the like.

Illustrative and non-limiting examples of cyclopentadienyl-indenylboron-bridged ligand compounds (with the alkenyl substituent on theindenyl group) can include the following compounds:

and the like.

Using analogous synthesis schemes to those provided herein, ligand andmetallocene complexes with substituents on the nitrogen other thanisopropyl can be derived, and complexes with cyclopentadienyl andfluorenyl groups with various alkenyl substituents (and optionally,other substituents) can be derived. Moreover, using analogous synthesisschemes to those provided herein, metallocene complexes with monoanionicligands other than Cl (e.g., hydrocarbyl, hydrocarbylaminyl,hydrocarbylsilyl, etc.) can be derived, and complexes with varioustransition metals can be derived.

Activator-Supports

The present invention encompasses various catalyst compositionscontaining an activator-support. In one aspect, the activator-supportcan comprise a solid oxide treated with an electron-withdrawing anion.Alternatively, in another aspect, the activator-support can comprise asolid oxide treated with an electron-withdrawing anion, the solid oxidecontaining a Lewis-acidic metal ion. Non-limiting examples of suitableactivator-supports are disclosed in, for instance, U.S. Pat. Nos.7,294,599, 7,601,665, 7,884,163, and 8,309,485, 8,623,973, and8,703,886, which are incorporated herein by reference in their entirety.

The solid oxide can encompass oxide materials such as alumina, “mixedoxides” thereof such as silica-alumina, coatings of one oxide onanother, and combinations and mixtures thereof. The mixed oxides such assilica-alumina can be single or multiple chemical phases with more thanone metal combined with oxygen to form the solid oxide. Examples ofmixed oxides that can be used to form an activator-support, eithersingly or in combination, can include, but are not limited to,silica-alumina, silica-titania, silica-zirconia, alumina-titania,alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria,aluminophosphate-silica, titania-zirconia, and the like. The solid oxideused herein also can encompass oxide materials such as silica-coatedalumina, as described in U.S. Pat. No. 7,884,163.

Accordingly, in one aspect, the solid oxide can comprise silica,alumina, silica-alumina, silica-coated alumina, aluminum phosphate,aluminophosphate, heteropolytungstate, titania, silica-titania,zirconia, silica-zirconia, magnesia, boria, zinc oxide, any mixed oxidethereof, or any combination thereof. In another aspect, the solid oxidecan comprise alumina, silica-alumina, silica-coated alumina, aluminumphosphate, aluminophosphate, heteropolytungstate, titania,silica-titania, zirconia, silica-zirconia, magnesia, boria, or zincoxide, as well as any mixed oxide thereof, or any mixture thereof. Inanother aspect, the solid oxide can comprise silica, alumina, titania,zirconia, magnesia, boria, zinc oxide, any mixed oxide thereof, or anycombination thereof. In yet another aspect, the solid oxide can comprisesilica-alumina, silica-coated alumina, silica-titania, silica-zirconia,alumina-boria, or any combination thereof. In still another aspect, thesolid oxide can comprise alumina, silica-alumina, silica-coated alumina,or any mixture thereof; alternatively, alumina; alternatively,silica-alumina; or alternatively, silica-coated alumina.

The silica-alumina or silica-coated alumina solid oxide materials whichcan be used can have an silica content from about 5 to about 95% byweight. In one aspect, the silica content of these solid oxides can befrom about 10 to about 80%, or from about 20% to about 70%, silica byweight. In another aspect, such materials can have silica contentsranging from about 15% to about 60%, or from about 25% to about 50%,silica by weight. The solid oxides contemplated herein can have anysuitable surface area, pore volume, and particle size, as would berecognized by those of skill in the art.

The electron-withdrawing component used to treat the solid oxide can beany component that increases the Lewis or Brønsted acidity of the solidoxide upon treatment (as compared to the solid oxide that is not treatedwith at least one electron-withdrawing anion). According to one aspect,the electron-withdrawing component can be an electron-withdrawing anionderived from a salt, an acid, or other compound, such as a volatileorganic compound, that serves as a source or precursor for that anion.Examples of electron-withdrawing anions can include, but are not limitedto, sulfate, bisulfate, fluoride, chloride, bromide, iodide,fluorosulfate, fluoroborate, phosphate, fluorophosphate,trifluoroacetate, triflate, fluorozirconate, fluorotitanate,phospho-tungstate, tungstate, molybdate, and the like, includingmixtures and combinations thereof. In addition, other ionic or non-ioniccompounds that serve as sources for these electron-withdrawing anionsalso can be employed. It is contemplated that the electron-withdrawinganion can be, or can comprise, fluoride, chloride, bromide, phosphate,triflate, bisulfate, or sulfate, and the like, or any combinationthereof, in some aspects provided herein. In other aspects, theelectron-withdrawing anion can comprise sulfate, bisulfate, fluoride,chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate,fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, and the like, or combinations thereof. Yet, in otheraspects, the electron-withdrawing anion can comprise fluoride and/orsulfate.

The activator-support generally can contain from about 1 to about 25 wt.% of the electron-withdrawing anion, based on the weight of theactivator-support. In particular aspects provided herein, theactivator-support can contain from about 1 to about 20 wt. %, from about2 to about 20 wt. %, from about 3 to about 20 wt. %, from about 2 toabout 15 wt. %, from about 3 to about 15 wt. %, from about 3 to about 12wt. %, or from about 4 to about 10 wt. %, of the electron-withdrawinganion, based on the total weight of the activator-support.

In an aspect, the activator-support can comprise fluorided alumina,chlorided alumina, bromided alumina, sulfated alumina, fluoridedsilica-alumina, chlorided silica-alumina, bromided silica-alumina,sulfated silica-alumina, fluorided silica-zirconia, chloridedsilica-zirconia, bromided silica-zirconia, sulfated silica-zirconia,fluorided silica-titania, fluorided silica-coated alumina, sulfatedsilica-coated alumina, phosphated silica-coated alumina, and the like,as well as any mixture or combination thereof. In another aspect, theactivator-support employed in the catalyst systems described herein canbe, or can comprise, a fluorided solid oxide and/or a sulfated solidoxide, non-limiting examples of which can include fluorided alumina,sulfated alumina, fluorided silica-alumina, sulfated silica-alumina,fluorided silica-zirconia, fluorided silica-coated alumina, sulfatedsilica-coated alumina, and the like, as well as combinations thereof. Inyet another aspect, the activator-support can comprise fluoridedalumina; alternatively, chlorided alumina; alternatively, sulfatedalumina; alternatively, fluorided silica-alumina; alternatively,sulfated silica-alumina; alternatively, fluorided silica-zirconia;alternatively, chlorided silica-zirconia; alternatively, sulfatedsilica-coated alumina; or alternatively, fluorided silica-coatedalumina.

Various processes can be used to form activator-supports useful in thepresent invention. Methods of contacting the solid oxide with theelectron-withdrawing component, suitable electron withdrawing componentsand addition amounts, impregnation with metals or metals ions (e.g.,zinc, nickel, vanadium, titanium, silver, copper, gallium, tin,tungsten, molybdenum, zirconium, and the like, or combinations thereof),and various calcining procedures and conditions are disclosed in, forexample, U.S. Pat. Nos. 6,107,230, 6,165,929, 6,294,494, 6,300,271,6,316,553, 6,355,594, 6,376,415, 6,388,017, 6,391,816, 6,395,666,6,524,987, 6,548,441, 6,548,442, 6,576,583, 6,613,712, 6,632,894,6,667,274, 6,750,302, 7,294,599, 7,601,665, 7,884,163, and 8,309,485,which are incorporated herein by reference in their entirety. Othersuitable processes and procedures for preparing activator-supports(e.g., fluorided solid oxides, sulfated solid oxides, etc.) are wellknown to those of skill in the art.

Co-Catalysts

In certain aspects directed to catalyst compositions containing aco-catalyst, the co-catalyst can comprise a metal hydrocarbyl compound,examples of which include non-halide metal hydrocarbyl compounds, metalhydrocarbyl halide compounds, non-halide metal alkyl compounds, metalalkyl halide compounds, and so forth. The hydrocarbyl group (or alkylgroup) can be any hydrocarbyl (or alkyl) group disclosed herein.Moreover, in some aspects, the metal of the metal hydrocarbyl can be agroup 1, 2, 11, 12, 13, or 14 metal; alternatively, a group 13 or 14metal; or alternatively, a group 13 metal. Hence, in some aspects, themetal of the metal hydrocarbyl (non-halide metal hydrocarbyl or metalhydrocarbyl halide) can be lithium, sodium, potassium, rubidium, cesium,beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, boron,aluminum, or tin; alternatively, lithium, sodium, potassium, magnesium,calcium, zinc, boron, aluminum, or tin; alternatively, lithium, sodium,or potassium; alternatively, magnesium or calcium; alternatively,lithium; alternatively, sodium; alternatively, potassium; alternatively,magnesium; alternatively, calcium; alternatively, zinc; alternatively,boron; alternatively, aluminum; or alternatively, tin. In some aspects,the metal hydrocarbyl or metal alkyl, with or without a halide, cancomprise a lithium hydrocarbyl or alkyl, a magnesium hydrocarbyl oralkyl, a boron hydrocarbyl or alkyl, a zinc hydrocarbyl or alkyl, or analuminum hydrocarbyl or alkyl.

In particular aspects directed to catalyst compositions containing aco-catalyst (e.g., the activator can comprise a solid oxide treated withan electron-withdrawing anion), the co-catalyst can comprise analuminoxane compound, an organoboron or organoborate compound, anionizing ionic compound, an organoaluminum compound, an organozinccompound, an organomagnesium compound, or an organolithium compound, andthis includes any combinations of these materials. In one aspect, theco-catalyst can comprise an organoaluminum compound. In another aspect,the co-catalyst can comprise an aluminoxane compound, an organoboron ororganoborate compound, an ionizing ionic compound, an organozinccompound, an organomagnesium compound, an organolithium compound, or anycombination thereof. In yet another aspect, the co-catalyst can comprisean aluminoxane compound; alternatively, an organoboron or organoboratecompound; alternatively, an ionizing ionic compound; alternatively, anorganozinc compound; alternatively, an organomagnesium compound; oralternatively, an organolithium compound.

Specific non-limiting examples of suitable organoaluminum compounds caninclude trimethylaluminum (TMA), triethylaluminum (TEA),tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA),triisobutylaluminum (TIBA), tri-n-hexylaluminum, tri-n-octylaluminum,diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminumchloride, and the like, or combinations thereof. Representative andnon-limiting examples of aluminoxanes include methylaluminoxane,modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane,iso-propylaluminoxane, n-butylaluminoxane, t-butylaluminoxane,sec-butylaluminoxane, iso-butylaluminoxane, 1 -pentylaluminoxane,2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane,neopentylaluminoxane, and the like, or any combination thereof.Representative and non-limiting examples of organoboron/organoboratecompounds include N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate,tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron,and the like, or mixtures thereof.

Examples of ionizing ionic compounds can include, but are not limitedto, the following compounds: tri(n-butyl)ammoniumtetrakis(p-tolyl)borate, tri(n-butyl) ammonium tetrakis(m-tolyl)borate,tri(n-butyl)ammonium tetrakis (2,4-dimethylphenyl)borate,tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate,tri(n-butyl)ammonium tetrakis [3,5-bis(trifluoromethyl)phenyl]borate,tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,N,N-dimethylanilinium tetrakis(p-tolyl)borate, N,N-dimethylaniliniumtetrakis(m-tolyl)borate, N,N-dimethylaniliniumtetrakis(2,4-dimethylphenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-dimethyl-phenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(p-tolyl)borate, triphenylcarbenium tetrakis(m-tolyl)borate,triphenylcarbenium tetrakis(2,4-dimethylphenyl)borate,triphenylcarbenium tetrakis(3,5-dimethylphenyl)borate,triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate,triphenylcarbenium tetrakis(pentafluorophenyl)borate, tropyliumtetrakis(p-tolyl)borate, tropylium tetrakis(m-tolyl)borate, tropyliumtetrakis(2,4-dimethylphenyl)borate, tropyliumtetrakis(3,5-dimethylphenyl)borate, tropyliumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tropyliumtetrakis(pentafluorophenyl) borate, lithiumtetrakis(pentafluorophenyl)borate, lithium tetraphenylborate, lithiumtetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate, lithiumtetrakis(2,4-dimethylphenyl)borate, lithiumtetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodiumtetrakis(pentafluorophenyl)borate, sodium tetraphenylborate, sodiumtetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodiumtetrakis(2,4-dimethylphenyl)borate, sodiumtetrakis(3,5-dimethyphenyl)borate, sodium tetrafluoroborate, potassiumtetrakis(pentafluorophenyl)borate, potassium tetraphenylborate,potassium tetrakis(p-tolyl)borate, potassium tetrakis(m-tolyl)borate,potassium tetrakis(2,4-dimethylphenyl)borate, potassiumtetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate, lithiumtetrakis(pentafluorophenyl)aluminate, lithium tetraphenylaluminate,lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate,lithium tetrakis(2,4-dimethylphenyl)aluminate, lithiumtetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate,sodium tetrakis(pentafluorophenyl)aluminate, sodiumtetraphenylaluminate, sodium tetrakis(p-tolyl)aluminate, sodiumtetrakis(m-tolyl)aluminate, sodiumtetrakis(2,4-dimethylphenyl)aluminate, sodiumtetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate,potassium tetrakis(pentafluorophenyl)aluminate, potassiumtetraphenylaluminate, potassium tetrakis(p-tolyl)aluminate, potassiumtetrakis(m-tolyl)aluminate, potassiumtetrakis(2,4-dimethylphenyl)aluminate, potassium tetrakis(3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate, and thelike, or combinations thereof.

Exemplary organozinc compounds which can be used as co-catalysts caninclude, but are not limited to, dimethylzinc, diethylzinc,dipropylzinc, dibutylzinc, dineopentylzinc, di(trimethylsilyl)zinc,di(triethylsilyl)zinc, di(triisoproplysilyl)zinc,di(triphenylsilyl)zinc, di(allyldimethylsilyl)zinc,di(trimethylsilylmethyl)zinc, and the like, or combinations thereof.

Similarly, exemplary organomagnesium compounds can include, but are notlimited to, dimethylmagnesium, diethylmagnesium, dipropylmagnesium,dibutylmagnesium, dineopentylmagnesium,di(trimethylsilylmethyl)magnesium, methylmagnesium chloride,ethylmagnesium chloride, propylmagnesium chloride, butylmagnesiumchloride, neopentylmagnesium chloride, trimethylsilylmethylmagnesiumchloride, methylmagnesium bromide, ethylmagnesium bromide,propylmagnesium bromide, butylmagnesium bromide, neopentylmagnesiumbromide, trimethylsilylmethylmagnesium bromide, methylmagnesium iodide,ethylmagnesium iodide, propylmagnesium iodide, butylmagnesium iodide,neopentylmagnesium iodide, trimethylsilylmethylmagnesium iodide,methylmagnesium ethoxide, ethylmagnesium ethoxide, propylmagnesiumethoxide, butylmagnesium ethoxide, neopentylmagnesium ethoxide,trimethylsilylmethylmagnesium ethoxide, methylmagnesium propoxide,ethylmagnesium propoxide, propylmagnesium propoxide, butylmagnesiumpropoxide, neopentylmagnesium propoxide, trimethylsilylmethylmagnesiumpropoxide, methylmagnesium phenoxide, ethylmagnesium phenoxide,propylmagnesium phenoxide, butylmagnesium phenoxide, neopentylmagnesiumphenoxide, trimethylsilylmethylmagnesium phenoxide, and the like, or anycombinations thereof.

Likewise, exemplary organolithium compounds can include, but are notlimited to, methyllithium, ethyllithium, propyllithium, butyllithium(e.g., t-butyllithium), neopentyllithium, trimethylsilylmethyllithium,phenyllithium, tolyllithium, xylyllithium, benzyllithium,(dimethylphenyl)methyllithium, allyllithium, and the like, orcombinations thereof.

Co-catalysts that can be used in the catalyst compositions of thisinvention are not limited to the co-catalysts described above. Othersuitable co-catalysts are well known to those of skill in the artincluding, for example, those disclosed in U.S. Pat. Nos. 3,242,099,4,794,096, 4,808,561, 5,576,259, 5,807,938, 5,919,983, 7,294,5997,601,665, 7,884,163, 8,114,946, and 8,309,485, which are incorporatedherein by reference in their entirety.

Olefin Monomers

Unsaturated reactants that can be employed with catalyst compositionsand polymerization processes of this invention typically can includeolefin compounds having from 2 to 30 carbon atoms per molecule andhaving at least one olefinic double bond. This invention encompasseshomopolymerization processes using a single olefin such as ethylene orpropylene, as well as copolymerization, terpolymerization, etc.,reactions using an olefin monomer with at least one different olefiniccompound. For example, the resultant ethylene copolymers, terpolymers,etc., generally can contain a major amount of ethylene (>50 molepercent) and a minor amount of comonomer (<50 mole percent), though thisis not a requirement. Comonomers that can be copolymerized with ethyleneoften can have from 3 to 20 carbon atoms, or from 3 to 10 carbon atoms,in their molecular chain.

Acyclic, cyclic, polycyclic, terminal (α), internal, linear, branched,substituted, unsubstituted, functionalized, and non-functionalizedolefins can be employed in this invention. For example, typicalunsaturated compounds that can be polymerized with the catalystcompositions of this invention can include, but are not limited to,ethylene, propylene, 1-butene, 2-butene, 3-methyl-l-butene, isobutylene,1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene,the four normal octenes (e.g., 1-octene), the four normal nonenes, thefive normal decenes, and the like, or mixtures of two or more of thesecompounds. Cyclic and bicyclic olefins, including but not limited to,cyclopentene, cyclohexene, norbornylene, norbornadiene, and the like,also can be polymerized as described herein. Styrene can also beemployed as a monomer in the present invention. In an aspect, the olefinmonomer can comprise a C₂-C₂₀ olefin; alternatively, a C₂-C₂₀alpha-olefin; alternatively, a C₂-C₁₀ olefin; alternatively, a C₂-C₁₀alpha-olefin; alternatively, the olefin monomer can comprise ethylene;or alternatively, the olefin monomer can comprise propylene.

When a copolymer (or alternatively, a terpolymer) is desired, the olefinmonomer and the olefin comonomer independently can comprise, forexample, a C₂-C₂₀ alpha-olefin. In some aspects, the olefin monomer cancomprise ethylene or propylene, which is copolymerized with at least onecomonomer (e.g., a C₂-C₂₀ alpha-olefin, a C₃-C₂₀ alpha-olefin, etc.).According to one aspect of this invention, the olefin monomer used inthe polymerization process can comprise ethylene. In this aspect,examples of suitable olefin comonomers can include, but are not limitedto, propylene, 1-butene, 2-butene, 3-methyl-l-butene, isobutylene,1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene,1-decene, styrene, and the like, or combinations thereof. According toanother aspect of the present invention, the olefin monomer can compriseethylene, and the comonomer can comprise a C₃-C₁₀ alpha-olefin;alternatively, the comonomer can comprise 1-butene, 1-pentene, 1-hexene,1-octene, 1-decene, styrene, or any combination thereof; alternatively,the comonomer can comprise 1-butene, 1-hexene, 1-octene, or anycombination thereof; alternatively, the comonomer can comprise 1-butene;alternatively, the comonomer can comprise 1-hexene; or alternatively,the comonomer can comprise 1-octene.

Generally, the amount of comonomer introduced into a polymerizationreactor system to produce a copolymer can be from about 0.01 to about 50weight percent of the comonomer based on the total weight of the monomerand comonomer. According to another aspect of the present invention, theamount of comonomer introduced into a polymerization reactor system canbe from about 0.01 to about 40 weight percent comonomer based on thetotal weight of the monomer and comonomer. In still another aspect, theamount of comonomer introduced into a polymerization reactor system canbe from about 0.1 to about 35 weight percent comonomer based on thetotal weight of the monomer and comonomer. Yet, in another aspect, theamount of comonomer introduced into a polymerization reactor system canbe from about 0.5 to about 20 weight percent comonomer based on thetotal weight of the monomer and comonomer.

While not intending to be bound by this theory, where branched,substituted, or functionalized olefins are used as reactants, it isbelieved that a steric hindrance can impede and/or slow thepolymerization process. Thus, branched and/or cyclic portion(s) of theolefin removed somewhat from the carbon-carbon double bond would not beexpected to hinder the reaction in the way that the same olefinsubstituents situated more proximate to the carbon-carbon double bondmight.

According to one aspect of the present invention, at least onemonomer/reactant can be ethylene (or propylene), so the polymerizationreaction can be a homopolymerization involving only ethylene (orpropylene), or a copolymerization with a different acyclic, cyclic,terminal, internal, linear, branched, substituted, or unsubstitutedolefin. In addition, the catalyst compositions of this invention can beused in the polymerization of diolefin compounds including, but notlimited to, 1,3-butadiene, isoprene, 1,4-pentadiene, and 1,5-hexadiene.

Catalyst Compositions

In some aspects, the present invention employs catalyst compositionscontaining a boron-bridged, cyclopentadienyl-fluorenyl metallocenecompound and an activator (one or more than one). These catalystcompositions can be utilized to produce polyolefins-homopolymers,copolymers, and the like—for a variety of end-use applications.Boron-bridged metallocene compounds are discussed hereinabove. Inaspects of the present invention, it is contemplated that the catalystcomposition can contain more than one boron-bridged metallocenecompound. Further, additional catalytic compounds—other than thosespecified as a boron-bridged metallocene compound—can be employed in thecatalyst compositions and/or the polymerization processes, provided thatthe additional catalytic compound does not detract from the advantagesdisclosed herein. Additionally, more than one activator also may beutilized.

Generally, catalyst compositions of the present invention comprise aboron-bridged metallocene compound having formula (I) and an activator.In aspects of the invention, the activator can comprise anactivator-support (e.g., an activator-support comprising a solid oxidetreated with an electron-withdrawing anion). Activator-supports usefulin the present invention are disclosed above. Optionally, such catalystcompositions can further comprise one or more than one co-catalystcompound or compounds (suitable co-catalysts, such as organoaluminumcompounds, also are discussed above). Thus, a catalyst composition ofthis invention can comprise a boron-bridged metallocene compound, anactivator-support, and an organoaluminum compound. For instance, theactivator-support can comprise (or consist essentially of, or consistof) fluorided alumina, chlorided alumina, bromided alumina, sulfatedalumina, fluorided silica-alumina, chlorided silica-alumina, bromidedsilica-alumina, sulfated silica-alumina, fluorided silica-zirconia,chlorided silica-zirconia, bromided silica-zirconia, sulfatedsilica-zirconia, fluorided silica-titania, fluorided silica-coatedalumina, sulfated silica-coated alumina, phosphated silica-coatedalumina, and the like, or combinations thereof; or alternatively, afluorided solid oxide and/or a sulfated solid oxide. Additionally, theorganoaluminum compound can comprise (or consist essentially of, orconsist of) trimethylaluminum, triethylaluminum, tri-n-propylaluminum,tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminumethoxide, diethylaluminum chloride, and the like, or combinationsthereof. Accordingly, a catalyst composition consistent with aspects ofthe invention can comprise (or consist essentially of, or consist of) aboron-bridged metallocene compound; sulfated alumina (or fluoridedsilica-alumina, or fluorided silica-coated alumina); andtriethylaluminum (or triisobutylaluminum).

In another aspect of the present invention, a catalyst composition isprovided which comprises a boron-bridged metallocene compound, anactivator-support, and an organoaluminum compound, wherein this catalystcomposition is substantially free of aluminoxanes, organoboron ororganoborate compounds, ionizing ionic compounds, and/or other similarmaterials; alternatively, substantially free of aluminoxanes;alternatively, substantially free or organoboron or organoboratecompounds; or alternatively, substantially free of ionizing ioniccompounds. In these aspects, the catalyst composition has catalystactivity, discussed below, in the absence of these additional materials.For example, a catalyst composition of the present invention can consistessentially a boron-bridged metallocene compound, an activator-support,and an organoaluminum compound, wherein no other materials are presentin the catalyst composition which would increase/decrease the activityof the catalyst composition by more than about 10% from the catalystactivity of the catalyst composition in the absence of said materials.

However, in other aspects of this invention, theseactivators/co-catalysts can be employed. For example, a catalystcomposition comprising a boron-bridged metallocene compound and anactivator-support can further comprise an optional co-catalyst. Suitableco-catalysts in this aspect can include, but are not limited to,aluminoxane compounds, organoboron or organoborate compounds, ionizingionic compounds, organoaluminum compounds, organozinc compounds,organomagnesium compounds, organolithium compounds, and the like, or anycombination thereof; or alternatively, organoaluminum compounds,organozinc compounds, organomagnesium compounds, organolithiumcompounds, or any combination thereof. More than one co-catalyst can bepresent in the catalyst composition.

In a different aspect, a catalyst composition is provided which does notrequire an activator-support. Such a catalyst composition can comprise aboron-bridged metallocene compound and an activator, wherein theactivator can comprise an aluminoxane compound, an organoboron ororganoborate compound, an ionizing ionic compound, or combinationsthereof; alternatively, an aluminoxane compound; alternatively, anorganoboron or organoborate compound; or alternatively, an ionizingionic compound.

In a particular aspect contemplated herein, the catalyst composition isa catalyst composition comprising an activator (one or more than one)and only one boron-bridged metallocene compound having formula (I). Inthese and other aspects, the catalyst composition can comprise anactivator (e.g., an activator-support comprising a solid oxide treatedwith an electron-withdrawing anion), only one boron-bridged metallocenecompound, and a co-catalyst (one or more than one), such as anorganoaluminum compound.

This invention further encompasses methods of making these catalystcompositions, such as, for example, contacting the respective catalystcomponents in any order or sequence. In one aspect, the catalystcomposition can be produced by a process comprising contacting themetallocene compound and the activator, while in another aspect, thecatalyst composition can be produced by a process comprising contacting,in any order, the metallocene compound, the activator, and theco-catalyst.

Generally, the weight ratio of organoaluminum compound toactivator-support can be in a range from about 10:1 to about 1:1000. Ifmore than one organoaluminum compound and/or more than oneactivator-support are employed, this ratio is based on the total weightof each respective component. In another aspect, the weight ratio of theorganoaluminum compound to the activator-support can be in a range fromabout 3:1 to about 1:100, or from about 1:1 to about 1:50.

In some aspects of this invention, the weight ratio of metallocenecompound to activator-support can be in a range from about 1:1 to about1:1,000,000. If more than one metallocene compound and/or more thanactivator-support is/are employed, this ratio is based on the totalweights of the respective components. In another aspect, this weightratio can be in a range from about 1:5 to about 1:100,000, or from about1:10 to about 1:10,000. Yet, in another aspect, the weight ratio of themetallocene compound to the activator-support can be in a range fromabout 1:20 to about 1:1000.

Catalyst compositions of the present invention generally have a catalystactivity greater than about 100,000 grams of ethylene polymer(homopolymer or copolymer, as the context requires) per gram of theboron-bridged metallocene compound per hour (abbreviated g/g/h). Inanother aspect, the catalyst activity can be greater than about 200,000,greater than about 250,000, or greater than about 500,000 g/g/h. Instill another aspect, catalyst compositions of this invention can becharacterized by having a homopolymer catalyst activity (or copolymercatalyst activity) greater than about 1,000,000, greater than about1,500,000, or greater than about 2,000,000 g/g/h, and often can range upto 3,000,000-4,000,000 g/g/h. These activities are measured under slurrypolymerization conditions, with a triisobutylaluminum co-catalyst, usingisobutane as the diluent, at a polymerization temperature of 80° C. anda reactor pressure of about 390 psig. Additionally, in some aspects, theactivator can comprise an activator-support, such as sulfated alumina,fluorided silica-alumina, or fluorided silica-coated alumina, althoughnot limited thereto.

Polymerization Processes

Catalyst compositions of the present invention can be used to polymerizeolefins to form homopolymers, copolymers, terpolymers, and the like. Onesuch process for polymerizing olefins in the presence of a catalystcomposition of the present invention can comprise contacting thecatalyst composition with an olefin monomer and optionally an olefincomonomer (one or more) in a polymerization reactor system underpolymerization conditions to produce an olefin polymer, wherein thecatalyst composition can comprise a boron-bridged metallocene compound,an activator, and an optional co-catalyst. Suitable boron-bridgedmetallocene compounds, activators, and co-catalysts are discussedherein.

In accordance with one aspect of the invention, the polymerizationprocess can employ a catalyst composition comprising a boron-bridgedmetallocene compound having formula (I) and an activator, wherein theactivator comprises an activator-support. The catalyst composition,optionally, can further comprise one or more than one organoaluminumcompound or compounds (or other suitable co-catalyst). Thus, a processfor polymerizing olefins in the presence of a catalyst composition canemploy a catalyst composition comprising a boron-bridged metallocenecompound, an activator-support, and an organoaluminum compound. In someaspects, the activator-support can comprise (or consist essentially of,or consist of) fluorided alumina, chlorided alumina, bromided alumina,sulfated alumina, fluorided silica-alumina, chlorided silica-alumina,bromided silica-alumina, sulfated silica-alumina, fluoridedsilica-zirconia, chlorided silica-zirconia, bromided silica-zirconia,sulfated silica-zirconia, fluorided silica-titania, fluoridedsilica-coated alumina, sulfated silica-coated alumina, phosphatedsilica-coated alumina, and the like, or combinations thereof; oralternatively, a fluorided solid oxide and/or a sulfated solid oxide. Insome aspects, the organoaluminum compound can comprise (or consistessentially of, or consist of) trimethylaluminum, triethylaluminum,tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride,diethylaluminum ethoxide, diethylaluminum chloride, and the like, orcombinations thereof.

In accordance with another aspect of the invention, the polymerizationprocess can employ a catalyst composition comprising a boron-bridgedmetallocene, an activator-support, and an optional co-catalyst, whereinthe co-catalyst can comprise an aluminoxane compound, an organoboron ororganoborate compound, an ionizing ionic compound, an organoaluminumcompound, an organozinc compound, an organomagnesium compound, or anorganolithium compound, or any combination thereof. Hence, aspects ofthis invention are directed to a process for polymerizing olefins in thepresence of a catalyst composition, the processes comprising contactinga catalyst composition with an olefin monomer and optionally an olefincomonomer (one or more) under polymerization conditions to produce anolefin polymer, and the catalyst composition can comprise aboron-bridged metallocene compound, an activator-support, and analuminoxane compound; alternatively, a boron-bridged metallocenecompound, an activator-support, and an organoboron or organoboratecompound; alternatively, a boron-bridged metallocene compound, anactivator-support, and an ionizing ionic compound; alternatively, aboron-bridged metallocene compound, an activator-support, and anorganoaluminum compound; alternatively, a boron-bridged metallocenecompound, an activator-support, and an organozinc compound;alternatively, a boron-bridged metallocene compound, anactivator-support, and an organomagnesium compound; or alternatively, aboron-bridged metallocene compound, an activator-support, and anorganolithium compound. Furthermore, more than one co-catalyst can beemployed, e.g., an organoaluminum compound and an aluminoxane compound,an organoaluminum compound and an ionizing ionic compound, etc.

In accordance with another aspect of the invention, the polymerizationprocess can employ a catalyst composition comprising only oneboron-bridged metallocene compound, an activator-support, and anorganoaluminum compound.

In accordance with yet another aspect of the invention, thepolymerization process can employ a catalyst composition comprising aboron-bridged metallocene compound and an activator, wherein theactivator comprises an aluminoxane compound, an organoboron ororganoborate compound, an ionizing ionic compound, or combinationsthereof; alternatively, an aluminoxane compound; alternatively, anorganoboron or organoborate compound; or alternatively, an ionizingionic compound.

The catalyst compositions of the present invention are intended for anyolefin polymerization method using various types of polymerizationreactor systems and reactors. The polymerization reactor system caninclude any polymerization reactor capable of polymerizing olefinmonomers and comonomers (one or more than one comonomer) to producehomopolymers, copolymers, terpolymers, and the like. The various typesof reactors include those that can be referred to as a batch reactor,slurry reactor, gas-phase reactor, solution reactor, high pressurereactor, tubular reactor, autoclave reactor, and the like, orcombinations thereof. Suitable polymerization conditions are used forthe various reactor types. Gas phase reactors can comprise fluidized bedreactors or staged horizontal reactors. Slurry reactors can comprisevertical or horizontal loops. High pressure reactors can compriseautoclave or tubular reactors. Reactor types can include batch orcontinuous processes. Continuous processes can use intermittent orcontinuous product discharge. Processes can also include partial or fulldirect recycle of unreacted monomer, unreacted comonomer, and/ordiluent.

Polymerization reactor systems of the present invention can comprise onetype of reactor in a system or multiple reactors of the same ordifferent type (e.g., a single reactor, dual reactor, more than tworeactors). Production of polymers in multiple reactors can includeseveral stages in at least two separate polymerization reactorsinterconnected by a transfer device making it possible to transfer thepolymers resulting from the first polymerization reactor into the secondreactor. The desired polymerization conditions in one of the reactorscan be different from the operating conditions of the other reactor(s).Alternatively, polymerization in multiple reactors can include themanual transfer of polymer from one reactor to subsequent reactors forcontinued polymerization. Multiple reactor systems can include anycombination including, but not limited to, multiple loop reactors,multiple gas phase reactors, a combination of loop and gas phasereactors, multiple high pressure reactors, or a combination of highpressure with loop and/or gas phase reactors. The multiple reactors canbe operated in series, in parallel, or both. Accordingly, the presentinvention encompasses polymerization reactor systems comprising a singlereactor, comprising two reactors, and comprising more than two reactors.The polymerization reactor system can comprise a slurry reactor, agas-phase reactor, a solution reactor, in certain aspects of thisinvention, as well as multi-reactor combinations thereof.

According to one aspect of the invention, the polymerization reactorsystem can comprise at least one loop slurry reactor comprising verticalor horizontal loops. Monomer, diluent, catalyst, and comonomer can becontinuously fed to a loop reactor where polymerization occurs.Generally, continuous processes can comprise the continuous introductionof monomer/comonomer, a catalyst, and a diluent into a polymerizationreactor and the continuous removal from this reactor of a suspensioncomprising polymer particles and the diluent. Reactor effluent can beflashed to remove the solid polymer from the liquids that comprise thediluent, monomer and/or comonomer. Various technologies can be used forthis separation step including, but not limited to, flashing that caninclude any combination of heat addition and pressure reduction,separation by cyclonic action in either a cyclone or hydrocyclone, orseparation by centrifugation.

A typical slurry polymerization process (also known as the particle formprocess) is disclosed, for example, in U.S. Pat. Nos. 3,248,179,4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191, and 6,833,415,each of which is incorporated herein by reference in its entirety.

Suitable diluents used in slurry polymerization include, but are notlimited to, the monomer being polymerized and hydrocarbons that areliquids under polymerization conditions. Examples of suitable diluentsinclude, but are not limited to, hydrocarbons such as propane,cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, andn-hexane. Some loop polymerization reactions can occur under bulkconditions where no diluent is used. An example is polymerization ofpropylene monomer as disclosed in U.S. Pat. Nos. 5,455,314, which isincorporated by reference herein in its entirety.

According to yet another aspect of this invention, the polymerizationreactor system can comprise at least one gas phase reactor. Such systemscan employ a continuous recycle stream containing one or more monomerscontinuously cycled through a fluidized bed in the presence of thecatalyst under polymerization conditions. A recycle stream can bewithdrawn from the fluidized bed and recycled back into the reactor.Simultaneously, polymer product can be withdrawn from the reactor andnew or fresh monomer can be added to replace the polymerized monomer.Such gas phase reactors can comprise a process for multi-step gas-phasepolymerization of olefins, in which olefins are polymerized in thegaseous phase in at least two independent gas-phase polymerization zoneswhile feeding a catalyst-containing polymer formed in a firstpolymerization zone to a second polymerization zone. One type of gasphase reactor is disclosed in U.S. Pat. Nos. 5,352,749, 4,588,790, and5,436,304, each of which is incorporated by reference in its entiretyherein.

According to still another aspect of the invention, a high pressurepolymerization reactor can comprise a tubular reactor or an autoclavereactor. Tubular reactors can have several zones where fresh monomer,initiators, or catalysts are added. Monomer can be entrained in an inertgaseous stream and introduced at one zone of the reactor. Initiators,catalysts, and/or catalyst components can be entrained in a gaseousstream and introduced at another zone of the reactor. The gas streamscan be intermixed for polymerization. Heat and pressure can be employedappropriately to obtain optimal polymerization reaction conditions.

According to yet another aspect of the invention, the polymerizationreactor system can comprise a solution polymerization reactor whereinthe monomer (and comonomer, if used) are contacted with the catalystcomposition by suitable stirring or other means. A carrier comprising aninert organic diluent or excess monomer can be employed. If desired, themonomer/comonomer can be brought in the vapor phase into contact withthe catalytic reaction product, in the presence or absence of liquidmaterial. The polymerization zone is maintained at temperatures andpressures that will result in the formation of a solution of the polymerin a reaction medium. Agitation can be employed to obtain bettertemperature control and to maintain uniform polymerization mixturesthroughout the polymerization zone. Adequate means are utilized fordissipating the exothermic heat of polymerization.

Polymerization reactor systems suitable for the present invention canfurther comprise any combination of at least one raw material feedsystem, at least one feed system for catalyst or catalyst components,and/or at least one polymer recovery system. Suitable reactor systemsfor the present invention can further comprise systems for feedstockpurification, catalyst storage and preparation, extrusion, reactorcooling, polymer recovery, fractionation, recycle, storage, loadout,laboratory analysis, and process control.

Polymerization conditions that are controlled for efficiency and toprovide desired polymer properties can include temperature, pressure,and the concentrations of various reactants. Polymerization temperaturecan affect catalyst productivity, polymer molecular weight, andmolecular weight distribution. A suitable polymerization temperature canbe any temperature below the de-polymerization temperature according tothe Gibbs Free energy equation. Typically, this includes from about 60°C. to about 280° C., for example, or from about 60° C. to about 120° C.,depending upon the type of polymerization reactor(s). In some reactorsystems, the polymerization temperature generally can fall within arange from about 70° C. to about 100° C., or from about 75° C. to about95° C. Various polymerization conditions can be held substantiallyconstant, for example, for the production of a particular grade ofolefin polymer.

Suitable pressures will also vary according to the reactor andpolymerization type. The pressure for liquid phase polymerizations in aloop reactor is typically less than 1000 psig (6.9 MPa). Pressure forgas phase polymerization is usually at about 200 to 500 psig (1.4 MPa to3.4 MPa). High pressure polymerization in tubular or autoclave reactorsis generally run at about 20,000 to 75,000 psig (138 to 517 MPa).Polymerization reactors can also be operated in a supercritical regionoccurring at generally higher temperatures and pressures. Operationabove the critical point of a pressure/temperature diagram(supercritical phase) may offer advantages.

Aspects of this invention are directed to olefin polymerizationprocesses comprising contacting a catalyst composition with an olefinmonomer and, optionally, an olefin comonomer under polymerizationconditions to produce an olefin polymer. The olefin polymer (e.g.,ethylene homopolymer, ethylene copolymer, etc.) produced by the processcan have any of the polymer properties disclosed herein, for example, adensity from about 0.91 to about 0.96 g/cm³, and/or less than about0.005 LCB per 1000 total carbon atoms, and/or a ratio of Mw/Mn fromabout 2 to about 8, and/or a ratio of Mz/Mw from about 1.5 to about 5,and/or a conventional or substantially flat comonomer distribution.

Aspects of this invention also are directed to olefin polymerizationprocesses conducted in the absence of added hydrogen. An olefinpolymerization process of this invention can comprise contacting acatalyst composition with an olefin monomer and optionally an olefincomonomer in a polymerization reactor system under polymerizationconditions to produce an olefin polymer, wherein the catalystcomposition can comprise a boron-bridged metallocene, an activator, andan optional co-catalyst, and wherein the polymerization process isconducted in the absence of added hydrogen (no hydrogen is added to thepolymerization reactor system). As one of ordinary skill in the artwould recognize, hydrogen can be generated in-situ by metallocenecatalyst compositions in various olefin polymerization processes, andthe amount generated can vary depending upon the specific catalystcomposition and metallocene compound employed, the type ofpolymerization process used, the polymerization reaction conditionsutilized, and so forth.

In other aspects, it may be desirable to conduct the polymerizationprocess in the presence of a certain amount of added hydrogen.Accordingly, an olefin polymerization process of this invention cancomprise contacting a catalyst composition with an olefin monomer andoptionally an olefin comonomer in a polymerization reactor system underpolymerization conditions to produce an olefin polymer, wherein thecatalyst composition comprises a boron-bridged metallocene, anactivator, and an optional co-catalyst, and wherein the polymerizationprocess is conducted in the presence of added hydrogen (hydrogen isadded to the polymerization reactor system). For example, the ratio ofhydrogen to the olefin monomer in the polymerization process can becontrolled, often by the feed ratio of hydrogen to the olefin monomerentering the reactor. The added hydrogen to olefin monomer ratio in theprocess can be controlled at a weight ratio which falls within a rangefrom about 25 ppm to about 1500 ppm, from about 50 to about 1000 ppm, orfrom about 100 ppm to about 750 ppm.

In a particular aspect and unexpectedly, the Mw/Mn ratio of the olefinpolymer produced by the process can increase as the amount of hydrogenadded to the polymerization reactor system increases. For instance, theMw/Mn ratio of the polymer produced by the process in absence of addedhydrogen (zero added hydrogen, molar ratio of H₂:olefin monomer equal tozero) can be less than the Mw/Mn of a polymer produced by the process inthe presence of hydrogen at a molar ratio of H₂:olefin monomer of 0.1:1,under the same polymerization conditions. In another aspect, the Mw/Mnratio of the polymer produced by the process in the presence of hydrogenat a molar ratio of H₂:olefin monomer equal to 0.1:1 can be less thanthe Mw/Mn of a polymer produced by the process in the presence ofhydrogen at a molar ratio of H₂:olefin monomer of 0.25:1, under the samepolymerization conditions. The same polymerization conditions means thatall components used to prepare the catalyst systems are held constant(e.g., same amount/type of metallocene compound, same amount/type ofco-catalyst, same amount/type of activator, such as fluoridedsilica-coated alumina, etc.) and all polymerization conditions are heldconstant (e.g., same polymerization temperature, same pressure, etc.).Hence, the only difference is the amount of hydrogen present during thepolymerization.

In some aspects of this invention, the feed or reactant ratio ofhydrogen to olefin monomer can be maintained substantially constantduring the polymerization run for a particular polymer grade. That is,the hydrogen:olefin monomer ratio can be selected at a particular ratiowithin a range from about 5 ppm up to about 1000 ppm or so, andmaintained at the ratio to within about +/−25% during the polymerizationrun. For instance, if the target ratio is 100 ppm, then maintaining thehydrogen:olefin monomer ratio substantially constant would entailmaintaining the feed ratio between about 75 ppm and about 125 ppm.Further, the addition of comonomer (or comonomers) can be, and generallyis, substantially constant throughout the polymerization run for aparticular polymer grade.

However, in other aspects, it is contemplated that monomer, comonomer(or comonomers), and/or hydrogen can be periodically pulsed to thereactor, for instance, in a manner similar to that employed in U.S. Pat.No. 5,739,220 and U.S. Patent Publication No. 2004/0059070, thedisclosures of which are incorporated herein by reference in theirentirety.

The concentration of the reactants entering the polymerization reactorsystem can be controlled to produce resins with certain physical andmechanical properties. The proposed end-use product that will be formedby the polymer resin and the method of forming that product ultimatelycan determine the desired polymer properties and attributes. Mechanicalproperties include tensile, flexural, impact, creep, stress relaxation,and hardness tests. Physical properties include density, molecularweight, molecular weight distribution, melting temperature, glasstransition temperature, temperature melt of crystallization, density,stereoregularity, crack growth, long chain branching, and rheologicalmeasurements.

This invention is also directed to, and encompasses, the polymersproduced by any of the polymerization processes disclosed herein.Articles of manufacture can be formed from, and/or can comprise, thepolymers produced in accordance with this invention.

Polymers and Articles

Olefin polymers encompassed herein can include any polymer produced fromany olefin monomer and optional comonomer(s) described herein. Forexample, the olefin polymer can comprise an ethylene homopolymer, anethylene copolymer (e.g., ethylene/α-olefin, ethylene/1-butene,ethylene/1-hexene, ethylene/1-octene, etc.), a propylene homopolymer, apropylene copolymer, an ethylene terpolymer, a propylene terpolymer, andthe like, including combinations thereof. In one aspect, the olefinpolymer can be an ethylene/1-butene copolymer, an ethylene/1-hexenecopolymer, or an ethylene/1-octene copolymer, while in another aspect,the olefin polymer can be an ethylene/1-hexene copolymer.

If the resultant polymer produced in accordance with the presentinvention is, for example, an ethylene polymer, its properties can becharacterized by various analytical techniques known and used in thepolyolefin industry. Articles of manufacture can be formed from, and/orcan comprise, the olefin polymers (e.g., ethylene polymers) of thisinvention, whose typical properties are provided below.

The densities of ethylene-based polymers produced using the catalystsystems and processes disclosed herein often are greater than or equalto about 0.89 g/cm³. In one aspect of this invention, the density of theethylene polymer can be in a range from about 0.89 to about 0.96 g/cm³.Yet, in another aspect, the density can be in a range from about 0.90 toabout 0.96 g/cm³, such as, for example, from about 0.91 to about 0.96g/cm³, from about 0.92 to about 0.95 g/cm³, or from about 0.91 to about0.94 g/cm³.

Ethylene polymers, such as homopolymers, copolymers, etc., consistentwith various aspects of the present invention generally have a ratio ofMw/Mn, or the polydispersity index, in a range from about 2 to about 12.In some aspects disclosed herein, the ratio of Mw/Mn can be in a rangefrom about 2 to about 8, from about 2 to about 6, or from about 2.5 toabout 5.5. In other aspects, the ratio of Mw/Mn can be in a range fromabout 2 to about 5, from about 2 to about 4, from about 2.2 to about 6,from about 2.2 to about 5, or from about 2.2 to about 3.8. Additionallyor alternatively, the ratio of Mz/Mw of the polymer can be in a rangefrom about 1.5 to about 5, from about 1.5 to about 4, from about 1.5 toabout 3, from about 1.7 to about 4.5, from about 1.8 to about 4, or fromabout 1.8 to about 2.8.

Generally, polymers produced in aspects of the present invention havelow levels of long chain branching, with typically less than about 0.01long chain branches (LCB) per 1000 total carbon atoms, and more often,less than about 0.008 LCB per 1000 total carbon atoms. In some aspects,the number of LCB per 1000 total carbon atoms can be less than about0.005, or less than about 0.003 LCB per 1000 total carbon atoms.Further, the olefin polymer can have less than about 0.002 LCB per 1000total carbon atoms in particular aspects of this invention.

Ethylene copolymers, for example, produced using the polymerizationprocesses and catalyst systems described hereinabove can, in someaspects, have a conventional comonomer distribution, generally, thelower molecular weight components of the polymer have higher comonomerincorporation than the higher molecular weight components. Typically,there is decreasing comonomer incorporation with increasing molecularweight. In one aspect, the number of short chain branches (SCB) per 1000total carbon atoms of the polymer can be greater at Mn than at Mw. Inanother aspect, the number of SCB per 1000 total carbon atoms of thepolymer can be greater at Mn than at Mz.

Yet, in other aspects, ethylene copolymers produced using thepolymerization processes and catalyst systems described hereinabove canhave a substantially flat comonomer distribution. For instance, thenumber of SCB per 1000 total carbon atoms of the polymer at Mn can bewithin +/−10-15% of the number of SCB per 1000 total carbon atoms at Mw.Additionally or alternatively, the number of SCB per 1000 total carbonatoms of the polymer at Mw can be within +/−10-15% of the number of SCBper 1000 total carbon atoms at Mz.

Polymers of ethylene, whether homopolymers, copolymers, and so forth,can be formed into various articles of manufacture. Articles which cancomprise polymers of this invention include, but are not limited to, anagricultural film, an automobile part, a bottle, a drum, a fiber orfabric, a food packaging film or container, a food service article, afuel tank, a geomembrane, a household container, a liner, a moldedproduct, a medical device or material, a pipe, a sheet or tape, a toy,and the like. Various processes can be employed to form these articles.Non-limiting examples of these processes include injection molding, blowmolding, rotational molding, film extrusion, sheet extrusion, profileextrusion, thermoforming, and the like. Additionally, additives andmodifiers are often added to these polymers in order to providebeneficial polymer processing or end-use product attributes. Suchprocesses and materials are described in Modern Plastics Encyclopedia,Mid-November 1995 Issue, Vol. 72, No. 12; and Film ExtrusionManual—Process, Materials, Properties, TAPPI Press, 1992; thedisclosures of which are incorporated herein by reference in theirentirety.

Applicants also contemplate a method for forming or preparing an articleof manufacture comprising a polymer produced by any of thepolymerization processes disclosed herein. For instance, a method cancomprise (i) contacting a catalyst composition with an olefin monomerand an optional olefin comonomer under polymerization conditions in apolymerization reactor system to produce an olefin polymer, wherein thecatalyst composition can comprise a boron-bridged metallocene, anactivator (e.g., an activator-support comprising a solid oxide treatedwith an electron-withdrawing anion), and an optional co-catalyst (e.g.,an organoaluminum compound); and (ii) forming an article of manufacturecomprising the olefin polymer. The forming step can comprise blending,melt processing, extruding, molding, or thermoforming, and the like,including combinations thereof.

EXAMPLES

The invention is further illustrated by the following examples, whichare not to be construed in any way as imposing limitations to the scopeof this invention. Various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, maysuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims.

Melt index (MI, g/10 min) was determined in accordance with ASTM D1238at 190° C. with a 2,160 gram weight. High load melt index (HLMI, g/10min) was determined in accordance with ASTM D1238 at 190° C. with a21,600 gram weight.

Polymer density was determined in grams per cubic centimeter (g/cm³) ona compression molded sample, cooled at about 15° C. per hour, andconditioned for about 40 hours at room temperature in accordance withASTM D1505 and ASTM D4703.

Molecular weights and molecular weight distributions were obtained usinga PL-GPC 220 (Polymer Labs, an Agilent Company) system equipped with aIR4 detector (Polymer Char, Spain) and three Styragel HMW-6E GPC columns(Waters, Mass.) running at 145° C. The flow rate of the mobile phase1,2,4-trichlorobenzene (TCB) containing 0.5 g/L2,6-di-t-butyl-4-methylphenol (BHT) was set at 1 mL/min, and polymersolution concentrations were in the range of 1.0-1.5 mg/mL, depending onthe molecular weight. Sample preparation was conducted at 150° C. fornominally 4 hr with occasional and gentle agitation, before thesolutions were transferred to sample vials for injection. An injectionvolume of about 200 μL was used. The integral calibration method wasused to deduce molecular weights and molecular weight distributionsusing a Chevron Phillips Chemicals Company's HDPE polyethylene resin,MARLEX® BHB5003, as the broad standard. The integral table of the broadstandard was pre-determined in a separate experiment with SEC-MALS. Mnis the number-average molecular weight, Mw is the weight-averagemolecular weight, and Mz is the z-average molecular weight.

Melt rheological characterizations were performed as follows.Small-strain (10%) oscillatory shear measurements were performed on aRheometrics Scientific, Inc. ARES rheometer using parallel-plategeometry. All rheological tests were performed at 190° C. The complexviscosity |η*| versus frequency (ω) data were then curve fitted usingthe modified three parameter Carreau-Yasuda (CY) empirical model toobtain the zero shear viscosity—η₀, characteristic viscous relaxationtime—τ_(η), and the breadth parameter13 α. The simplified Carreau-Yasuda(CY) empirical model is as follows.

${{{\eta^{*}(\omega)}} = \frac{\eta_{0}}{\left\lbrack {1 + \left( {\tau_{\eta}\omega} \right)^{a}} \right\rbrack^{{({1 - n})}/a}}},$

wherein: |η*(ω)|32 magnitude of complex shear viscosity;

-   -   η₀=zero shear viscosity;    -   τ_(η)=viscous relaxation time (Tau(η));    -   α=“breadth” parameter (CY-a parameter);    -   n=fixes the final power law slope, fixed at 2/11; and

ω=angular frequency of oscillatory shearing deformation.

Details of the significance and interpretation of the CY model andderived parameters may be found in: C. A. Hieber and H. H. Chiang,Rheol. Acta, 28, 321 (1989); C. A. Hieber and H. H. Chiang, Polym. Eng.Sci., 32, 931 (1992); and R. B. Bird, R. C. Armstrong and O. Hasseger,Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2nd Edition,John Wiley & Sons (1987); each of which is incorporated herein byreference in its entirety.

The long chain branches (LCB) per 1000 total carbon atoms werecalculated using the method of Janzen and Colby (J. Mol. Struct.,485/486, 569-584 (1999)), from values of zero shear viscosity, η_(o)(determined from the Carreau-Yasuda model), and measured values of Mwobtained using a Dawn EOS multiangle light scattering detector (Wyatt).See also U.S. Pat. No. 8,114,946; J. Phys. Chem. 1980, 84, 649; and Y.Yu, D. C. Rohlfing, G. R Hawley, and P. J. DesLauriers, PolymerPreprint, 44, 50, (2003). These references are incorporated herein byreference in their entirety.

Short chain branch (SCB) content and short chain branching distribution(SCBD) across the molecular weight distribution were determined via anIR5-detected GPC system (IR5-GPC), wherein the GPC system was a PL220GPC/SEC system (Polymer Labs, an Agilent company) equipped with threeStyragel HMW-6E columns (Waters, Mass.) for polymer separation. Athermoelectric-cooled IR5 MCT detector (IRS) (Polymer Char, Spain) wasconnected to the GPC columns via a hot-transfer line. Chromatographicdata were obtained from two output ports of the IR5 detector. First, theanalog signal goes from the analog output port to a digitizer beforeconnecting to Computer “A” for molecular weight determinations via theCirrus software (Polymer Labs, now an Agilent Company) and the integralcalibration method using a broad MWD HDPE Marlex™ BHB5003 resin (ChevronPhillips Chemical) as the broad molecular weight standard. The digitalsignals, on the other hand, go via a USB cable directly to Computer “B”where they are collected by a LabView data collection software providedby Polymer Char. Chromatographic conditions were set as follows: columnoven temperature of 145° C.; flowrate of 1 mL/min; injection volume of0.4 mL; and polymer concentration of about 2 mg/mL, depending on samplemolecular weight. The temperatures for both the hot-transfer line andIR5 detector sample cell were set at 150° C., while the temperature ofthe electronics of the IRS detector was set at 60° C. Short chainbranching content was determined via an in-house method using theintensity ratio of CH₃ (I_(CH3)) to CH₂ (I_(CH2)) coupled with acalibration curve. The calibration curve was a plot of SCB content(x_(SCB)) as a function of the intensity ratio of I_(CH3)/I_(CH2). Toobtain a calibration curve, a group of polyethylene resins (no less than5) of SCB level ranging from zero to ca. 32 SCB/1,000 total carbons (SCBStandards) were used. All these SCB Standards have known SCB levels andflat SCBD profiles pre-determined separately by NMR and thesolvent-gradient fractionation coupled with NMR (SGF-NMR) methods. UsingSCB calibration curves thus established, profiles of short chainbranching distribution across the molecular weight distribution wereobtained for resins fractionated by the IR5-GPC system under exactly thesame chromatographic conditions as for these SCB standards. Arelationship between the intensity ratio and the elution volume wasconverted into SCB distribution as a function of MWD using apredetermined SCB calibration curve (i.e., intensity ratio ofI_(CH3)/I_(CH2) vs. SCB content) and MW calibration curve (i.e.,molecular weight vs. elution time) to convert the intensity ratio ofI_(CH3)/I_(CH2) and the elution time into SCB content and the molecularweight, respectively.

Fluorided silica-coated aluminas were prepared as follows. Alumina A,from W. R. Grace Company, was impregnated to incipient wetness was firstcalcined in dry air at about 600° C. for approximately 6 hours, cooledto ambient temperature, and then contacted with tetraethylorthosilicatein isopropanol to equal 25 wt. % SiO₂. After drying, the silica-coatedalumina was calcined at 600° C. for 3 hours. Fluorided silica-coatedalumina (7 wt. % F) was prepared by impregnating the calcinedsilica-coated alumina with an ammonium bifluoride solution in methanol,drying, and then calcining for 3 hours at 600° C. (unless otherwisenoted) in dry air. Afterward, the fluorided silica-coated alumina wascollected and stored under dry nitrogen, and was used without exposureto the atmosphere.

Example 1

In Example 1, metallocene MET-A, shown below, was synthesized by firstreacting sodium cyclopentadiene with 5-bromo-1-pentene, to form apentenyl substituted cyclopentadiene, which was isolated in good yield.One mole of this compound was lithiated and reacted with one mole ofdichloro(diisopropylamino) borane in diethyl ether at −78° C. Theresulting solution was warmed to 20° C. for 12 hr, then cooled downagain to −78° C., and then a diethyl ether solution of lithiated2,7-di-tert-butylfluorine was added. The resulting orange slurry wasstirred for 12 hr while warming to 20° C. The solvent was removed underreduced pressure, and the resulting dark red/orange oil was removed in10 mL of pentane (this solution was then placed in a freezer at −34° C.for 12 hr). The ligand shown below was isolated as an orange solid:

A portion of the ligand product was mixed with diethyl ether and cooledto −34° C., and then mixed with a diethyl ether solution of lithiumdiisopropylamine, resulting in a bright orange slurry, followed bywarming to 20° C. while stirring. A suspension of ZrCl₄ in diethyl etherwas cooled to −34° C., following by addition of the ligand mixture.After first turning dark orange, the resultant slurry then turned tobright orange. After stirring for 12 hr and warming to 20° C., thesolvent was removed under reduced pressure, and the resultant orangesolid was extracted with methylene chloride. After filtering to isolatethe solid, the remaining solvent was removed at reduced pressure,resulting in MET-A as a bright orange solid {¹H NMR (300 MHz C₆D₆): δ7.567-8.00 (4H, m), 7.024 (2H, m), 6.24 (1H, t), 5.58-5.779 (1H, m),5.304 (1H, t), 4.825-5.137 (3H, m), 2.533 (2H, s), 0.737-1.782 (36H,m)}:

EXAMPLE 2

Using a synthesis procedure analogous to that of Example 1, thefollowing ligand compound and metallocene compound (MET-B) were produced{mixture of rac/meso isomers—¹H NMR (300 MHz, C₆D₆): δ 7.26-7.34 (2H,m), 7.12-7.20 (2H, m), 6.94-7.03 (2H, m), 6.69-6.77 (2H, m), 5.69-5.80(2H, m), 5.405 (1H, d), 5.22 (1H, s), 5.01 (1H, d), 4.97 (1H, d),3.758-3.935 (2.76H, m), 2.95-3.08 (2.35H, m), 2.80-2.94 (2.55H, m), 2.02(3.40H, m), 1.55-1.71 (3.77H, m), 1.07-1.26 (13.54H, m)}:

Examples 3-5

Using a synthesis procedure analogous to that of Example 1, thefollowing ligand compounds were produced:

Examples 6-9

Examples 6-9 were produced using the following polymerization procedure.All polymerization runs were conducted in a one-gallon stainless steelreactor. Isobutane (1.2 L) was used in all runs. A metallocene solutionof MET-A was prepared at about 1 mg/mL in toluene. Approximately 100 mgof fluorided silica-coated alumina, 0.5 mmol of alkyl aluminum(triisobutylaluminum), and the metallocene solution (containing 2 mg ofMET-A) were added in that order through a charge port while slowlyventing isobutane vapor. The charge port was closed and isobutane wasadded. The contents of the reactor were stirred and heated to thedesired run temperature of about 80° C., and ethylene was thenintroduced into the reactor with 10 g (Example 6), 20 g (Example 7), 30g (Example 8), or 40 g (Example 9) of 1-hexene. Ethylene was fed ondemand to maintain the target pressure of 390 psig pressure for thelength of the polymerization run, which was varied to producesubstantially the same amount of polymer (about 150 g). The reactor wasmaintained at the desired run temperature throughout the run by anautomated heating-cooling system. The catalyst activity for Examples 6-9ranged from 200,000 to 600,000 grams of polymer per gram of MET-A perhour.

FIGS. 1-4 illustrate the molecular weight distributions and short chainbranch distributions of the polymers of Examples 6-9, respectively,while Table I summarizes various molecular weight and other polymerproperty characteristics for the polymers of Examples 6-9. In additionto relatively high molecular weights and narrow molecular weightdistributions, the polymers of Examples 6-7 and 9 had a substantiallyflat comonomer distribution, while the polymer of Example 8 exhibited aconventional (decreasing) comonomer distribution (e.g., there arerelatively more short chain branches (SCB) at the lower molecularweights; assumes 2 methyl chain ends (CE)). In FIG. 3, the number of SCBper 1000 total carbon (TC) atoms of the polymer at Mz (or Mw) is lessthan at Mn.

TABLE I Polymer Properties of Examples 6-9. Example 6 7 8 9 MI (g/10min) 0 0 0 0 HLMI (g/10 min) 0.06 0.14 0.27 0.34 Density (g/cm³) 0.9200.939 0.930 0.915 Mn (kg/mol) 142 101 125 127 Mw (kg/mol) 365 329 304307 Mz (kg/mol) 690 617 552 542 Mw/Mn 2.57 3.26 2.43 2.41 Mz/Mw 1.891.88 1.81 1.77

Example 10

Example 10 was performed in substantially the same manner as Examples6-9 using MET-A, with the exception that no comonomer was used (i.e., anethylene homopolymer was produced). Table II summarizes certainproperties of the homopolymer of Example 10. The catalyst activity wasabout 500,000 grams of polymer per gram of MET-A per hour. As shown inTable II, the homopolymer of Example 10 had a high molecular weight,narrow molecular weight distribution, and a relatively low density foran ethylene homopolymer. The homopolymer of Example 10 also had very lowlevels of long chain branches (LCB), i.e., less than 0.005 per 1000total carbon atoms. FIG. 5 illustrates the very low amount of LCB of thehomopolymer of Example 10 produced using MET-A as a function of thepolymer molecular weight.

TABLE II Homopolymer Properties of Example 10. Example 10 MI (g/10 min)0 HLMI (g/10 min) <0.1 Density (g/cm³) 0.924 Mn (kg/mol) 204 Mw (kg/mol)479 Mz (kg/mol) 950 Mw/Mn 2.35 Mz/Mw 1.98 LCB/1000 TC's <0.005

Examples 11-13

Examples 11-13 were performed in substantially the same manner asExample 10, with the exception that certain amounts of hydrogen wereadded during polymerization (hydrogen was added with the ethylene feedat the specified percentage). FIG. 6 illustrates that the addition ofhydrogen reduced the average polymer molecular weight (e.g., shiftingcurves to the left as hydrogen addition increased). Unexpectedly,however, the addition of hydrogen also broadened the molecular weightdistribution (e.g., increased Mw/Mn), as summarized in Table III for thehydrogen:ethylene molar ratios used in Examples 11-13.

TABLE III Hydrogen Impact on Molecular Weight Distribution. Example 1112 13 H₂:ethylene 0 0.1:1 0.25:1 Mw/Mn 2.3 6.0 11.0

Examples 14-16

Examples 14-16 were performed in substantially the same manner asExamples 6-9 using MET-A, with the exception that certain molar ratiosof 1-hexene:ethylene were used during polymerization. As shown in TableIV, and unexpectedly, the catalyst system containing MET-A provided goodcomonomer incorporation, as illustrated by the relatively large drop indensity based on the increase in the comonomer:monomer molar ratio.

TABLE IV Comonomer 1-Hexene Impact on Density. Example 14 15 161-hexene:ethylene 0.034 0.068 0.140 Density (g/cm³) 0.9236 0.9176 0.9146

The invention is described above with reference to numerous aspects andembodiments, and specific examples. Many variations will suggestthemselves to those skilled in the art in light of the above detaileddescription. All such obvious variations are within the full intendedscope of the appended claims. Other embodiments of the invention caninclude, but are not limited to, the following (embodiments aredescribed as “comprising” but, alternatively, can “consist essentiallyof” or “consist of”):

Embodiment 1. A ligand compound having the formula:

wherein:Cp^(A) is a cyclopentadienyl group with an alkenyl substituent; Cp^(B)is a fluorenyl group; and each R independently is H, a C₁ to C₃₆hydrocarbyl group, or a C₁ to C₃₆ hydrocarbylsilyl group.

Embodiment 2. A metallocene compound having the formula:

wherein: M is Ti, Zr, or Hf; each X independently is a monoanionicligand; Cp^(A) is a cyclopentadienyl group with an alkenyl substituent;Cp^(B) is a fluorenyl group; and each R independently is H, a C₁ to C₃₆hydrocarbyl group, or a C₁ to C₃₆ hydrocarbylsilyl group.

Embodiment 3. The compound defined in embodiment 1 or 2, wherein Cp^(A)is a cyclopentadienyl group with an alkenyl substituent, and Cp^(B) is afluorenyl group that does not have an alkenyl substituent.

Embodiment 4. The compound defined in embodiment 1 or 2, wherein Cp^(A)is a cyclopentadienyl group with an alkenyl substituent, and Cp^(B) is afluorenyl group with an alkenyl substituent.

Embodiment 5. The compound defined in any one of embodiments 1-4,wherein Cp^(A) is a cyclopentadienyl group with one alkenyl substituent.

Embodiment 6. The compound defined in any one of embodiments 1-5,wherein the alkenyl substituent is any alkenyl group disclosed herein,e.g., a C₂ to C₁₈ alkenyl group.

Embodiment 7. The compound defined in any one of embodiments 1-6,wherein the alkenyl substituent is an ethenyl group, a propenyl group, abutenyl group, a pentenyl group, a hexenyl group, a heptenyl group, anoctenyl group, a nonenyl group, or a decenyl group.

Embodiment 8. The compound defined in any one of embodiments 1-6,wherein the alkenyl substituent is a C₃ to C₁₂ linear alkenyl group.

Embodiment 9. The compound defined in any one of embodiments 1-6,wherein the alkenyl substituent is a C₃ to C₈ terminal alkenyl group(e.g., a C₃ to C₆ terminal alkenyl group).

Embodiment 10. The compound defined in any one of embodiments 1-9,wherein Cp^(A) contains a substituent (one or more) in addition to thealkenyl substituent, e.g., H, a halide, a C₁ to C₃₆ hydrocarbyl group, aC₁ to C₃₆ halogenated hydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group,or a C₁ to C₃₆ hydrocarbylsilyl group.

Embodiment 11. The compound defined in any one of embodiments 1-10,wherein Cp^(B) contains a substituent (one or more), e.g., H, a halide,a C₁ to C₃₆ hydrocarbyl group, a C₁ to C₃₆ halogenated hydrocarbylgroup, a C₁ to C₃₆ hydrocarboxy group, or a C₁ to C₃₆ hydrocarbylsilylgroup.

Embodiment 12. The compound defined in embodiment 10 or 11, wherein thesubstituent (or each substituent independently) is H or a C₁ to C₁₈hydrocarbyl group.

Embodiment 13. The compound defined in embodiment 10 or 11, wherein thesubstituent (or each substituent independently) is H, Cl, CF₃, a methylgroup, an ethyl group, a propyl group, a butyl group, a pentyl group, ahexyl group, a heptyl group, an octyl group, a nonyl group, a decylgroup, an ethenyl group, a propenyl group, a butenyl group, a pentenylgroup, a hexenyl group, a heptenyl group, an octenyl group, a nonenylgroup, a decenyl group, a phenyl group, a tolyl group, a benzyl group, anaphthyl group, a trimethylsilyl group, a triisopropylsilyl group, atriphenylsilyl group, an allyldimethylsilyl group, or a1-methylcyclohexyl group.

Embodiment 14. The compound defined in embodiment 10 or 11, wherein thesubstituent (or each substituent independently) is a C₁ to C₆ linear orbranched alkyl group (e.g., a tert-butyl group).

Embodiment 15. The compound defined in any one of embodiments 1-14,wherein each R independently is H or any C₁ to C₁₈ hydrocarbyl group orC₁ to C₁₈ hydrocarbylsilyl group disclosed herein.

Embodiment 16. The compound defined in any one of embodiments 1-14,wherein each R independently is a methyl group, an ethyl group, a propylgroup, a butyl group, a pentyl group, a hexyl group, a heptyl group, anoctyl group, a nonyl group, a decyl group, a phenyl group, a tolylgroup, a benzyl group, a naphthyl group, a trimethylsilyl group, atriisopropylsilyl group, a triphenylsilyl group, an allyldimethylsilylgroup, or a 1-methylcyclohexyl group.

Embodiment 17. The compound defined in any one of embodiments 1-14,wherein each R independently is a C₁ to C₆ linear or branched alkylgroup (e.g., an isopropyl group).

Embodiment 18. The compound defined in any one of embodiments 2-17,wherein M is Ti.

Embodiment 19. The compound defined in any one of embodiments 2-17,wherein M is Zr.

Embodiment 20. The compound defined in any one of embodiments 2-17,wherein M is Hf

Embodiment 21. The compound defined in any one of embodiments 2-20,wherein each X independently is any monoanionic ligand disclosed herein.

Embodiment 22. The compound defined in any one of embodiments 2-21,wherein each X independently is H, BH₄, a halide, a C₁ to C₃₆hydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, a C₁ to C₃₆hydrocarbylaminyl group, a C₁ to C₃₆ hydrocarbylsilyl group, a C₁ to C₃₆hydrocarbylaminylsilyl group, OBR¹ ₂, or OSO₂R¹, wherein R¹ is a C₁ toC₃₆ hydrocarbyl group.

Embodiment 23. The compound defined in any one of embodiments 2-22,wherein each X independently is any halide or C₁ to C₁₈ hydrocarbylgroup disclosed herein.

Embodiment 24. The compound defined in any one of embodiments 2-23,wherein each X is Cl.

Embodiment 25. A catalyst composition comprising the metallocenecompound defined in any one of embodiments 2-24, an activator, and anoptional co-catalyst.

Embodiment 26. The composition defined in embodiment 25, wherein theactivator comprises any activator disclosed herein.

Embodiment 27. The composition defined in embodiment 25 or 26, whereinthe activator comprises an aluminoxane compound, an organoboron ororganoborate compound, an ionizing ionic compound, or any combinationthereof.

Embodiment 28. The composition defined in any one of embodiments 25-27,wherein the activator comprises an aluminoxane compound.

Embodiment 29. The composition defined in any one of embodiments 25-27,wherein the activator comprises an organoboron or organoborate compound.

Embodiment 30. The composition defined in any one of embodiments 25-27,wherein the activator comprises an ionizing ionic compound.

Embodiment 31. The composition defined in embodiment 25 or 26, whereinthe activator comprises an activator-support, the activator-supportcomprising any solid oxide treated with an electron-withdrawing aniondisclosed herein.

Embodiment 32. The composition defined in embodiment 31, wherein thesolid oxide comprises any solid oxide disclosed herein, e.g., silica,alumina, silica-alumina, silica-coated alumina, aluminum phosphate,aluminophosphate, heteropolytungstate, titania, zirconia, magnesia,boria, zinc oxide, a mixed oxide thereof, or any mixture thereof; andthe electron-withdrawing anion comprises any electron-withdrawing aniondisclosed herein, e.g., sulfate, bisulfate, fluoride, chloride, bromide,iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate,trifluoroacetate, triflate, fluorozirconate, fluorotitanate,phospho-tungstate, or any combination thereof.

Embodiment 33. The composition defined in embodiment 31, wherein theactivator-support comprises fluorided alumina, chlorided alumina,bromided alumina, sulfated alumina, fluorided silica-alumina, chloridedsilica-alumina, bromided silica-alumina, sulfated silica-alumina,fluorided silica-zirconia, chlorided silica-zirconia, bromidedsilica-zirconia, sulfated silica-zirconia, fluorided silica-titania,fluorided silica-coated alumina, sulfated silica-coated alumina,phosphated silica-coated alumina, or any combination thereof.

Embodiment 34. The composition defined in embodiment 31, wherein theactivator-support comprises fluorided alumina, sulfated alumina,fluorided silica-alumina, sulfated silica-alumina, fluoridedsilica-coated alumina, sulfated silica-coated alumina, or anycombination thereof.

Embodiment 35. The composition defined in embodiment 31, wherein theactivator-support comprises a fluorided solid oxide, a sulfated solidoxide, or any combination thereof.

Embodiment 36. The composition defined in embodiment 31, wherein theactivator-support further comprises any metal or metal ion disclosedherein, e.g., zinc, nickel, vanadium, titanium, silver, copper, gallium,tin, tungsten, molybdenum, zirconium, or any combination thereof.

Embodiment 37. The composition defined in embodiment 25 or 26, whereinthe activator comprises an activator-support, the activator-supportcomprising a clay mineral, a pillared clay, an exfoliated clay, anexfoliated clay gelled into another oxide matrix, a layered silicatemineral, a non-layered silicate mineral, a layered aluminosilicatemineral, a non-layered aluminosilicate mineral, or any combinationthereof.

Embodiment 38. The composition defined in any one of embodiments 25-37,wherein the catalyst composition comprises a co-catalyst, e.g., anyco-catalyst disclosed herein.

Embodiment 39. The composition defined in any one of embodiments 25-38,wherein the co-catalyst comprises an organoaluminum compound, anorganozinc compound, an organomagnesium compound, an organolithiumcompound, or any combination thereof.

Embodiment 40. The composition defined in any one of embodiments 25-39,wherein the co-catalyst comprises an organoaluminum compound.

Embodiment 41. The composition defined in embodiment 40, wherein theorganoaluminum compound comprises any organoaluminum compound disclosedherein, e.g., trimethylaluminum, triethylaluminum, triisobutylaluminum,etc., or combinations thereof.

Embodiment 42. The composition defined in any one of embodiments 31-41,wherein the catalyst composition is substantially free of aluminoxanecompounds, organoboron or organoborate compounds, ionizing ioniccompounds, or combinations thereof.

Embodiment 43. The composition defined in any one of embodiments 31-41,wherein the co-catalyst comprises an aluminoxane compound, anorganoboron or organoborate compound, an ionizing ionic compound, anorganoaluminum compound, an organozinc compound, an organomagnesiumcompound, an organolithium compound, or any combination thereof.

Embodiment 44. The composition defined in any one of embodiments 25-43,wherein the catalyst composition comprises any compound having formula(I) disclosed herein.

Embodiment 45. The composition defined in any one of embodiments 25-44,wherein the catalyst composition comprises only one compound havingformula (I).

Embodiment 46. The composition defined in any one of embodiments 25-45,wherein the catalyst composition is produced by a process comprisingcontacting the metallocene compound and the activator.

Embodiment 47. The composition defined in any one of embodiments 25-46,wherein the catalyst composition is produced by a process comprisingcontacting, in any order, the metallocene compound, the activator, andthe co-catalyst.

Embodiment 48. The composition defined in any one of embodiments 25-47,wherein a catalyst activity of the catalyst composition is in any rangedisclosed herein, e.g., greater than about 100,000 grams, greater thanabout 200,000 grams, greater than about 500,000 grams, etc., of ethylenepolymer per gram of metallocene compound per hour, under slurrypolymerization conditions, with a triisobutylaluminum co-catalyst, usingisobutane as a diluent, and with a polymerization temperature of 80° C.and a reactor pressure of 390 psig.

Embodiment 49. An olefin polymerization process, the process comprisingcontacting the catalyst composition defined in any one of embodiments25-48 with an olefin monomer and an optional olefin comonomer in apolymerization reactor system under polymerization conditions to producean olefin polymer.

Embodiment 50. The process defined in embodiment 49, wherein the olefinmonomer comprises any olefin monomer disclosed herein, e.g., any C₂-C₂₀olefin.

Embodiment 51. The process defined in embodiment 49 or 50, wherein theolefin monomer and the optional olefin comonomer independently comprisea C₂-C₂₀ alpha-olefin.

Embodiment 52. The process defined in any one of embodiments 49-51,wherein the olefin monomer comprises ethylene.

Embodiment 53. The process defined in any one of embodiments 49-52,wherein the catalyst composition is contacted with ethylene and anolefin comonomer comprising a C₃-C₁₀ alpha-olefin.

Embodiment 54. The process defined in any one of embodiments 49-53,wherein the catalyst composition is contacted with ethylene and anolefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixturethereof.

Embodiment 55. The process defined in any one of embodiments 49-51,wherein the olefin monomer comprises propylene.

Embodiment 56. The process defined in any one of embodiments 49-55,wherein the polymerization reactor system comprises a batch reactor, aslurry reactor, a gas-phase reactor, a solution reactor, a high pressurereactor, a tubular reactor, an autoclave reactor, or a combinationthereof.

Embodiment 57. The process defined in any one of embodiments 49-56,wherein the polymerization reactor system comprises a slurry reactor, agas-phase reactor, a solution reactor, or a combination thereof.

Embodiment 58. The process defined in any one of embodiments 49-57,wherein the polymerization reactor system comprises a loop slurryreactor.

Embodiment 59. The process defined in any one of embodiments 49-58,wherein the polymerization reactor system comprises a single reactor.

Embodiment 60. The process defined in any one of embodiments 49-58,wherein the polymerization reactor system comprises 2 reactors.

Embodiment 61. The process defined in any one of embodiments 49-58,wherein the polymerization reactor system comprises more than 2reactors.

Embodiment 62. The process defined in any one of embodiments 49-61,wherein the olefin polymer comprises any olefin polymer disclosedherein.

Embodiment 63. The process defined in any one of embodiments 49-62,wherein the olefin polymer is an ethylene homopolymer, anethylene/1-butene copolymer, an ethylene/1-hexene copolymer, or anethylene/1-octene copolymer.

Embodiment 64. The process defined in any one of embodiments 49-63,wherein the olefin polymer is an ethylene/1-hexene copolymer.

Embodiment 65. The process defined in any one of embodiments 49-62,wherein the olefin polymer is a polypropylene homopolymer or apropylene-based copolymer.

Embodiment 66. The process defined in any one of embodiments 49-65,wherein the polymerization conditions comprise a polymerization reactiontemperature in a range from about 60° C. to about 120° C. and a reactionpressure in a range from about 200 to about 1000 psig (about 1.4 toabout 6.9 MPa).

Embodiment 67. The process defined in any one of embodiments 49-66,wherein the polymerization conditions are substantially constant, e.g.,for a particular polymer grade.

Embodiment 68. The process defined in any one of embodiments 49-67,wherein no hydrogen is added to the polymerization reactor system.

Embodiment 69. The process defined in any one of embodiments 49-67,wherein hydrogen is added to the polymerization reactor system.

Embodiment 70. The process defined in any one of embodiments 49-67,wherein the ratio of Mw/Mn of the olefin polymer increases as the amountof hydrogen added to the polymerization reactor system increases, e.g.,the Mw/Mn ratio of the polymer produced by the process in pressure ofzero added hydrogen is less than the Mw/Mn of a polymer produced by theprocess in the presence of hydrogen at a molar ratio of H₂:olefinmonomer of 0.1:1; the Mw/Mn ratio of the polymer produced by the processin the presence of hydrogen at a molar ratio of H₂:olefin monomer equalto 0.1:1 is less than the Mw/Mn of a polymer produced by the process inthe presence of hydrogen at a molar ratio of H₂:olefin monomer of0.25:1; etc., under the same polymerization conditions.

Embodiment 71. The process defined in any one of embodiments 49-70,wherein the olefin polymer has a density in any range disclosed herein,e.g., from about 0.89 to about 0.96, from about 0.91 to about 0.96, fromabout 0.92 to about 0.95 g/cm³, etc.

Embodiment 72. The process defined in any one of embodiments 49-71,wherein the olefin polymer has less than about 0.01 long chain branches(LCB) per 1000 total carbon atoms, e.g., less than about 0.008 LCB per1000 total carbon atoms, less than about 0.005 LCB per 1000 total carbonatoms, less than about 0.003 LCB per 1000 total carbon atoms, etc.

Embodiment 73. The process defined in any one of embodiments 49-72,wherein the olefin polymer has a ratio of Mw/Mn in any range disclosedherein, e.g., from about 2 to about 12, from about 2 to about 8, fromabout 2 to about 5, from about 2 to about 4, etc.

Embodiment 74. The process defined in any one of embodiments 49-73,wherein the olefin polymer has a ratio of Mz/Mw in any range disclosedherein, e.g., from about 1.5 to about 5, from about 1.5 to about 3, fromabout 1.8 to about 2.8, etc.

Embodiment 75. The process defined in any one of embodiments 49-74,wherein the olefin polymer has a conventional comonomer distribution,e.g., the number of short chain branches (SCB) per 1000 total carbonatoms at Mn is greater than Mw and/or the number of SCB per 1000 totalcarbon atoms at Mn is greater than at Mz, etc.

Embodiment 76. The process defined in any one of embodiments 49-74,wherein the olefin polymer has a substantially flat comonomerdistribution.

Embodiment 77. The process defined in any one of embodiments 49-76,wherein the olefin polymer (e.g., an ethylene/1-hexene copolymer) has adecrease in density in any range disclosed herein, based on an increasein comonomer:monomer molar ratio (e.g., 1-hexene:ethylene molar ratio)from 0.034 to 0.068, e.g., a decrease in density of at least about 0.002g/cm³ (up to about 0.009-0.010 g/cm³), at least about 0.003 g/cm³, atleast about 0.004 g/cm³, at least about 0.005 g/cm³, etc.

Embodiment 78. An olefin polymer produced by the olefin polymerizationprocess defined in any one of embodiments 49-77.

Embodiment 79. An article comprising the olefin polymer defined inembodiment 78.

Embodiment 80. A method or forming or preparing an article ofmanufacture comprising an olefin polymer, the method comprising (i)performing the olefin polymerization process defined in any one ofembodiments 49-77 to produce an olefin polymer, and (ii) forming thearticle of manufacture comprising the olefin polymer, e.g., via anytechnique disclosed herein.

Embodiment 81. The article defined in any one of embodiments 79-80,wherein the article is an agricultural film, an automobile part, abottle, a drum, a fiber or fabric, a food packaging film or container, afood service article, a fuel tank, a geomembrane, a household container,a liner, a molded product, a medical device or material, a pipe, a sheetor tape, or a toy.

1-10. (canceled).
 11. A catalyst composition comprising a metallocenecompound, an activator, and an optional co-catalyst, wherein themetallocene compound has the formula:

wherein: M is Ti, Zr, or Hf; each X independently is a monoanionicligand; Cp^(A) is a cyclopentadienyl group with an alkenyl substituent;Cp^(B) is a fluorenyl group; and each R independently is H, a C₁ to C₃₆hydrocarbyl group, or a C₁ to C₃₆ hydrocarbylsilyl group.
 12. Thecomposition of claim 11, wherein: M is Zr or Hf; each X independently isa halide or a C₁ to C₁₈ hydrocarbyl group; Cp^(B) is a substitutedfluorenyl group; and each R independently is H or a C₁ to C₁₈hydrocarbyl group.
 13. The composition of claim 11, wherein: M is Zr orHf; each X independently is Cl, methyl, phenyl, or benzyl; Cp^(A) is acyclopentadienyl group with only one alkenyl substituent; Cp^(B) is asubstituted fluorenyl group; and each R independently is a C₁ to C₆alkyl group.
 14. The composition of claim 11, wherein the catalystcomposition comprises an organoaluminum co-catalyst, and wherein theactivator comprises an activator-support, the activator-supportcomprising fluorided alumina, sulfated alumina, fluoridedsilica-alumina, sulfated silica-alumina, fluorided silica-coatedalumina, sulfated silica-coated alumina, or any combination thereof. 15.The composition of claim 11, wherein the activator comprises anactivator-support, the activator-support comprising a solid oxidetreated with an electron-withdrawing anion.
 16. The composition of claim15, wherein: a catalyst activity of the catalyst composition is greaterthan about 100,000 grams of ethylene polymer per gram of the metallocenecompound per hour, under slurry polymerization conditions, with atriisobutylaluminum co-catalyst, using isobutane as a diluent, and witha polymerization temperature of 80° C. and a reactor pressure of 390psig.
 17. The composition of claim 11, wherein the activator comprisesan aluminoxane compound, an organoboron or organoborate compound, anionizing ionic compound, or any combination thereof.
 18. A metallocenecompound having the formula:

wherein: M is Ti, Zr, or Hf; each X independently is a monoanionicligand; Cp^(A) is a cyclopentadienyl group with an alkenyl substituent;Cp^(B) is a fluorenyl group; and each R independently is H, a C₁ to C₃₆hydrocarbyl group, or a C₁ to C₃₆ hydrocarbylsilyl group.
 19. Thecompound of claim 18, wherein: M is Zr or Hf; each X independently is ahalide or a C₁ to C₁₈ hydrocarbyl group; and each R independently is Hor a C₁ to C₁₈ hydrocarbyl group.
 20. The compound of claim 18, wherein:M is Zr or Hf; each X independently is Cl, methyl, phenyl, or benzyl;and each R independently is a C₁ to C₆ alkyl group.
 21. The compound ofclaim 18, wherein the alkenyl substituent is a C₃ to C₈ terminal alkenylgroup.
 22. The compound of claim 18, wherein: each X independently is ahalide or a C₁ to C₁₈ hydrocarbyl group; Cp^(B) is a substitutedfluorenyl group; and each R independently is H or a C₁ to C₁₈hydrocarbyl group.
 23. The compound of claim 18, wherein: each Xindependently is Cl, methyl, phenyl, or benzyl; Cp^(A) is acyclopentadienyl group with one alkenyl substituent; Cp^(B) is asubstituted fluorenyl group; and each R independently is a C₁ to C₆alkyl group.
 24. The compound of claim 18, wherein: Cp^(A) is acyclopentadienyl group with one C₃ to C₈ terminal alkenyl substituent;and Cp^(B) is a fluorenyl group with two C₁ to C₆ linear or branchedalkyl substituents.
 25. The compound of claim 18, wherein: each X is Cl;and each R independently is H or a C₁ to C₁₈ hydrocarbyl group.
 26. Thecompound of claim 25, wherein: M is Zr or Hf; the alkenyl substituent isa C₃ to C₈ terminal alkenyl group; Cp^(B) is a substituted fluorenylgroup; and each R independently is C₁ to C₆ linear or branched alkylgroup.
 27. The composition of claim 11, wherein: the catalystcomposition comprises an organoaluminum co-catalyst; and the activatorcomprises a fluorided solid oxide and/or a sulfated solid oxide.
 28. Thecomposition of claim 27, wherein: M is Zr or Hf; each X independently isa halide or a C₁ to C₁₈ hydrocarbyl group; the alkenyl substituent is aC₃ to C₈ terminal alkenyl group; Cp^(B) is a substituted fluorenylgroup; and each R independently is H or a C₁ to C₁₈ hydrocarbyl group.29. The composition of claim 11, wherein the activator comprises analuminoxane compound.
 30. The composition of claim 29, wherein: M is Zror Hf; each X independently is a halide or a C₁ to C₁₈ hydrocarbylgroup; the alkenyl substituent is a C₃ to C₈ terminal alkenyl group;Cp^(B) is a substituted fluorenyl group; and each R independently is Hor a C₁ to C₁₈ hydrocarbyl group.